Synthesis and liquid crystalline studies of biphenylyl-1,3,4-thiadiazoles and diphenyl-1,3,4-thiadiazoles:

Influence of side chain semifluorination and lateral ring fluorination

Farid S. Fouad1,*, Melati Khairuddean1,2 and Robert J. Twieg1

1
Department of Chemistry and Biochemistry, Kent State University, 1175 Risman Drive, Kent, Ohio 44242
2
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia
*Email: ffouad@kent.edu

Synthesis of 4’-ethylbiphenyl-4-carboxylic acid hydrazides, 24a

In a 500 ml recovery flask equipped with stir bar, condenser and nitrogen inlet containing methyl 4’-

ethylbiphenyl-4-carboxylate[1] (4.5 gm, 18.75 mmol) was placed methanol (50 ml) and

tetrahydrofuran (50 ml). Hydrazine hydrate (8.85 gm, 150 mmol) was added, and the reaction was

stirred at room temperature overnight. Little reaction occurred and so the flask was fitted with a solvent

stripper and heated to a gentle reflux. After ~40 ml of solvent was removed TLC indicated the reaction

was complete. The mixture was cooled and water (~400 ml) was added dropwise with stirring. The

solid product was isolated by suction filtration, washed well with water and air dried. Yield = 90%; 1H

NMR (400 MHz, DMSO-d6): 9.82 (s, 1H), 7.92 (d, J=8.9 Hz, 2H), 7.73 (d, J=8.4 Hz, 2H), 7.64 (d,

J=8.4 Hz, 2H), 7.32 (d, J=8.4 Hz, 2H), 4.53 (bs, 2H), 2.26 (q, J=7.6 Hz,, 2H); 1.21 (t, J=7.6 Hz, 3H).
13
C-NMR (100 MHz): 166.04, 144.19, 143.03, 137.05, 132.29, 128.90, 128.04, 127.22, 126.73, 28.28,

16.00 ppm.

Synthesis of 4’-hexyloxybiphenyl-4-carboxylic acid hydrazides, 24b

A 100 mL round bottom flask was charged with 4-bromobenzhydrazide (0.3 g, 1.5 mmol), 4-

hexyloxyphenylboronic acid (0.5 g, 2.0 mmol), toluene (20 mL), and ethanol (5 mL). The contents of
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the flask were stirred under nitrogen until the solid reagents were dissolved. The flask was charged

with sodium carbonate (0.3 g, 2.0 mmol) and tetrakis(triphenylphosphine)palladium (17.0 mg, 1

mol%), and was heated with stirring at 90 °C overnight. Reaction completion was observed by TLC,

noting disappearance of the spot for 4-bromobenzhydrazide and the appearance of a new spot for the

product. The flask was cooled to room temperature, and the solvent was removed under vacuum.

Water (~90 mL) was added and the crude product was dried by vacuum filtration. Crude yield: 0.53

g. The crude product was recrystallized from ethyl acetate giving the purified product as white crystals

(0.30 g, 65%); mp 186-187 °C. 1H-NMR (400 MHz, DMSO): 7.81 (d, 2H); 7.65 (d, 2H), 7.56 (d, 2H),

7.39 (t, 1H), 7.01 (d, 2H),4.14 (d, 2H), 4.03 (t, 2H), 1.83 (p, 2H), 1.49 (p, 2H), 1.39 (p, 4H), 0.94 (t,

3H). IR (Neat): 3286, 2937, 2863, 1604, 1580, 1254, 1181, 995, 829 cm-1. 13
C-NMR (100 MHz,

CDCl3): 168.5, 159.4, 144.5, 132.0, 130.5, 128.2, 127.3, 126.8, 114.9, 68.2, 31.6, 29.2, 25.7, 22.6, 14.1

ppm.

General synthesis of diacylhydrazines, 25a-g. A solution of 4’-substitutedbiphenyl-4-carboxylic

acid hydrazide (1.0 eq, 3.0 mmol) and TEA (2.0 eq, 6 mmol) in DCM (15 ml) was cooled to 0 °C

under N2 gas. Respected acid anhydride or acid chloride (1.1 eq, 3.3 mmol) was added dropwise. The

mixture was allowed to worm to room temperature and continue to stir for 20 hours. The crude product

was collected by filtration, washed by water, and recrystallized from methanol/water.

N-(4’-Ethyl -biphenyl-4-carbonyl)-N’-acetyl hydrazine, 25a.

Yield, 76%. 1H NMR (400 MHz, DMSO-d6) 10.33 (s, 1H), 9.91 (s, 1H), 7.96 (d, J=8.4 Hz, 2H), 7.87

(d, J=8.8 Hz, 2H), 7.66 (d, J=8.4 Hz, 2H), 7.34 (d, J=8.4 Hz, 2H), 2.67 (q, J=7.6 Hz, 2H), 1.95 (s, 3H),

1.22 (t, J=7.6 Hz, 3H).

N-(4’-Ethyl -biphenyl-4-carbonyl)-N’-propanoyl hydrazine, 25b.

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Yield, 82%. 1H NMR (400 MHz, DMSO-d6) 10.32 (s, 1H), 9.87 (s, 1H), 7.96 (d, J=8.4 Hz, 2H), 7.87

(d, J=8.8 Hz, 2H), 7.66 (d, J=8.0 Hz, 2H), 7.33 (d, J=8.4 Hz, 2H), 2.67 (q, J=7.6 Hz, 2H), 2.23 (q, J=7.6

Hz, 2H), 1.22 (t, J=7.2 Hz, 3H) 1.08 (t, J=7.6 Hz, 3H).

N-(4’-Ethyl -biphenyl-4-carbonyl)-N’-butanoyl hydrazine, 25c.

Yield, 87%. 1H NMR (400 MHz, DMSO-d6) 10.35 (s, 1H), 9.88 (s, 1H), 7.98 (d, J=8.8 Hz, 2H), 7.78

(d, J=8.8 Hz, 2H), 7.66 (d, J=8.4 Hz, 2H), 7.33 (d, J=8.4 Hz, 2H), 2.67 (q, J=7.6 Hz, 2H), 2.19 (t, J=7.2

Hz, 2H), 1.61 (sex, J=7.6 Hz, 2H), 1.22 (t, J=7.6 Hz, 3H), 0.95 (t, J=7.2 Hz, 3H).

N-(4’-Ethyl -biphenyl-4-carbonyl)-N’-pentanoyl hydrazine, 25d.

Yield, 79%. 1H NMR (400 MHz, DMSO-d6) 10.34 (s, 1H), 9.87 (s, 1H), 7.96 (d, J=8.4 Hz, 2H), 7.78

(d, J=8.4 Hz, 2H), 7.67 (d, J=8.4 Hz, 2H), 7.34 (d, J=8.4 Hz, 2H), 2.67 (q, J=7.6 Hz, 2H), 2.20 (t, J=7.2

Hz, 2H), 1.56 (qn, J=7.2 Hz, 2H), 1.38 (sex, J=7.6 Hz, 2H), 1.24 (t, J=7.6 Hz, 3H), 0.91 (t, J=7.2 Hz,

3H).

N-(4’-Ethyl -biphenyl-4-carbonyl)-N’-octanoyl hydrazine, 25e.

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Yield, 92%. 1H NMR (400 MHz, DMSO-d6) 10.31 (s, 1H), 9.84 (s, 1H), 7.97 (d, J=8.4 Hz, 2H), 7.78

(d, J=8.4 Hz, 2H), 7.66 (d, J=8.0 Hz, 2H), 7.34 (d, J=8.0 Hz, 2H), 2.67 (q, J=7.6 Hz, 2H), 2.19 (t, J=7.2

Hz, 2H), 1.60 (qn, J=6.8 Hz, 2H), 1.34-1.20 (m, 11H), 0.88 (t, J=6.4 Hz, 3H).

N-(4’-Hexyloxy -biphenyl-4-carbonyl)-N’-butanoyl hydrazine, 25f.

Yield, 88%. 1H NMR (400 MHz, DMSO-d6) 10.34 (s, 1H), 9.87 (s, 1H), 7.96 (d, J=8.0 Hz, 2H), 7.75

(d, J=8.0 Hz, 2H), 7.68 (d, J=8.4 Hz, 2H), 7.04 (d, J=8.4 Hz, 2H), 4.01 (t, J=6.4 Hz, 2H), 2.18 (t, J=7.2

Hz, 2H), 1.73 (m, 2H), 1.60 (m, 2H), 1.43-1.31 (m, 6H), 0.96-0.88 (m, 6H).

N-(4’-Hexyloxy -biphenyl-4-carbonyl)-N’-pentanoyl hydrazine, 25g.

Yield, 83%. 1H NMR (400 MHz, DMSO-d6) 10.29 (s, 1H), 9.83 (s, 1H), 7.95 (d, J=8.4 Hz, 2H), 7.75

(d, J=8.4 Hz, 2H), 7.69 (d, J=8.8 Hz, 2H), 7.04 (d, J=8.8 Hz, 2H), 4.02 (t, J=6.4 Hz, 2H), 2.20 (t, J=7.2

Hz, 2H), 1.71 (qn, J=6.8 Hz, 2H), 1.57 (qn, J=7.2 Hz, 2H), 1.47-1.31 (m, 8H), 0.92-0.89 (m, 6H).

Synthesis of methyl 4-(n-alkyloxy)benzoates.[1,2] Methyl p- hydroxybenzoate (5.00 g, 32.86 mmol)

and potassium carbonate (13.60 g, 0.10 mmol) were combined in 20.0 ml of DMF under nitrogen

atmosphere and then 1-bromononane (7.49 g, 36.15 mmol) was added and the mixture was refluxed.

The reaction was monitored by TLC. After 20 h the reaction mixture was cooled to room temperature

and poured into 200 ml of ice water. After acidification, the product was collected by vacuum filtration,

recrystallized from methanol/water and dried in the oven at 60°C to give the expected product.

Methyl 4-(n-nonyloxy)benzoate.

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Yield = 92%. 1H NMR (400 MHz, CDCl3) 7.97 (dd, J=6.8, 2.0 Hz, 2H), 6.89 (dd, J=6.8, 2.0 Hz,

2H), 4.00 (t, J=6.6 Hz, 2H), 3.87 (s, 3H), 1.79 (q, J=6.8 Hz, 2H), 1.40-1.50 (m, 2H), 1.22––1.38 (m,

10H), 0.88 (t, J=7.0 Hz, 3H). 13C NMR (CDCl3) 14.09, 22.66, 25.98, 29.12, 29.24, 29.36, 29.51,

31.86, 51.80, 68.22, 114.08, 122.32, 131.56, 162.98, 166.93. IR (cm-1) 2800, 1724, 1607, 1510, 1257,

1170, 1106, 1020.

Methyl 4-(n-decyloxy)benzoate.

Yield = 96%. 1H NMR (400 MHz, CDCl3) 7.96 (dd, J=6.8, 2.0 Hz, 2H), 6.88 (dd, J=6.8, 2.0 Hz, 2H),

3.98 (t, J=6.4 Hz, 2H), 3.86 (s, 3H), 1.76-1.80 (m, 2H), 1.42-1.46 (m, 2H), 1.26––1.33 (m, 12H), 0.87

(t, J=6.8 Hz, 3H). 13C NMR (CDCl3) 14.12, 22.69, 25.99, 29.12, 29.32, 29.37, 29.55, 29.56, 31.90,

51.81, 68.21, 114.06, 122.31, 131.56, 162.97, 166.92. IR (cm-1) 2800, 1723, 1607, 1510, 1257, 1169,

1106, 1020.

Methyl 4-(n-dodecyloxy)benzoate.

Yield = 98%. 1H NMR (400 MHz, CDCl3) 7.96 (dd, J=7.2, 2.0 Hz, 2H), 6.88 (dd, J=6.8, 2.0 Hz,

2H), 3.98 (t, J=6.6 Hz, 2H), 3.86 (s, 3H), 1.76-1.79 (m, 2H), 1.42-1.46 (m, 2H), 1.25––1.35 (m, 16H),

0.87 (t, J=6.8 Hz, 3H). 13C NMR (CDCl3) 14.12, 22.70, 25.99, 29.12, 29.36, 29.57, 29.59, 29.60,

29.64, 29.66, 31.93, 51.81, 68.20, 114.06, 122.30, 131.56, 162.97, 166.92. IR (cm-1) 2802, 1723,

1607, 1510, 1257, 1169, 1108,1021.

Synthesis of 4-(n-alkyloxy)benzoic acids.[2] The preparation of 4-(n- nonyloxy)benzoic acid 1a is

provided as a general example: A mixture of methyl 4-(n- nonyloxy) benzoate (3.00 g, 10.0 mmol)
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in 10 N aqueous KOH (20.0 ml), 95% EtOH (80.0 ml) and THF (20.0 ml) in a round bottom flask

was refluxed. A white solid forms, but dissolves when the mixture is heated. Upon completion

(TLC), the mixture was cooled to room temperature and acidified. The product was collected by

vacuum filtration, recrystallized from methanol/water and dried in the oven at 60 °C to give the white

flakes.

4-(n-Nonyloxy)benzoic acid.

Yield = 95%. 1H NMR (400 MHz, CDCl3) 8.06 (d, J=8.4 Hz, 2H), 6.94 (d, J=8.4 Hz, 2H), 4.03 (t,

J=6.6 Hz, 2H), 1.82 (q, J=6.8 Hz, 2H), 1.44-1.51 (m, 2H), 1.21––1.39 (m, 10H), 0.90 (t, J=6.8 Hz, 3H).
13
C NMR (CDCl3) 14.11, 22.68, 25.99, 29.10, 29.26, 29.37, 29.52, 31.88, 68.31, 114.20, 121.40,

132.35, 163.72, 172.06. IR (cm-1) 3433-3015, 2920, 2850, 1734, 1558, 1508, 1177, 1124, 1018, 940,

846.

4-(n-decyloxy)benzoic acid.

Yield = 91%. 1H NMR (400 MHz, CDCl3) 8.05 (dd, J=6.8, 2.0 Hz, 2H), 6.92 (dd, J=6.8, 2.0 Hz,

2H), 4.02 (t, J=6.6 Hz, 2H), 1.76-1.84 (m, 2H), 1.41-1.50 (m, 2H), 1.22––1.38 (m, 12H), 0.88 (t, J=6.8

Hz, 3H). 13C NMR (CDCl3) 14.12, 22.69, 25.99, 29.10, 29.32, 29.36, 29.55, 29.56, 31.90, 68.30,

114.20, 121.36, 132.35, 163.72, 171.90. IR (cm-1) 3430-3010, 2916, 2820, 1683, 1605, 1469, 1305,

1256, 1167, 936, 845, 771.

4-(n-dodecyloxy)benzoic acid.

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Yield = 94%. 1H NMR (400 MHz, CDCl3) 8.05 (dd, J=7.0, 2.2 Hz, 2H), 6.93 (dd, J=6.8, 2.0 Hz, 2H), 4.02 (t,

J=6.6 Hz, 2H), 1.76-1.85 (m, 2H), 1.41-1.51 (m, 2H), 1.22–– 1.39 (m, 16H), 0.88 (t, J=6.8 Hz, 3H). 13C NMR (400

MHz, CDCl3) 14.13, 22.70, 25.98, 29.09, 29.36, 29.56, 29.59, 29.63, 29.64, 29.66, 31.92, 68.30, 114.21, 121.00,

132.34, 164.00, 171.40. IR (cm-1) 3450-3040, 2914, 2847, 1672, 1606, 1513, 1469, 1306, 1257, 1172, 939, 845,

771.

Synthesis of 4-n-(fluoroalkyloxy)benzoic acids. All these semifluorinated benzoic acids were

synthesized for earlier studies by an established method.[3-8]

4-n-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyloxy)benzoic acid.

1H NMR (400 MHz, CDCl3) 8.07 (dd, J=11.4, 2.6 Hz, 2H), 6.96 (dd, J=8.8, 2.8 Hz, 2H), 4.14 (t, J=6.0 Hz, 2H),

2.28-2.41 (m, 2H), 2.12-2.19 (m, 2H). 13C NMR (400 MHz,CDCl3) 20.64, 28.04 (d, J=22.1 Hz, CF2CH2-), 66.68

(CH2O), 110-120 (m, CF3(CF2)5), 114.28, 122.16, 132.34, 163.0 (aromatic), 170.1 (PhCOOH). IR (cm-1) 3430-

3020, 2980, 2890, 1672, 1606, 1515, 1450, 1252, 1175, 1140, 1025

4-n-(7,7,8,8,9,9,10,10,10-nonafluorodecyloxy)benzoic acid.

1H NMR (400 MHz, CDCl ) 8.06 (dd, J=6.8, 2.0 Hz, 2H), 6.94 (dd, J=7.0, 1.8 Hz, 2H), 4.04 (t, J=6.4 Hz, 2H),
3

2.01-2.16 (m, 2H), 1.81-1.88 (m, 2H), 1.62-1.70 (m, 2H), 1.44- 1.58 (m, 4H). 13C NMR (400 MHz, CDCl3) 20.08,

25.73, 28.82, 29.00, 34.10 (d, J=22.1 Hz, CF2CH2-), 67.95 (-CH2O-), 110-120 (m, CF3(CF2)3), 114.18, 125.50,

132.36, 163.50 (aromatic), 172.00 (PhCOOH). IR (cm-1) 3320-3030, 2980, 2895, 1667, 1605, 1514, 1434, 1214,

1173, 1130.

4-n-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-pentadecafluorodecyloxy)benzoic acid.

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1H NMR (400 MHz, CDCl ) 8.06 (d, J=8.8 Hz, 2H), 6.95 (d, J=8.8 Hz, 2H), 4.13 (t, J=6.0 Hz, 2H), 2.27-2.41
3

(m, 2H), 2.12-2.19 (m, 2H). 13C NMR (400 MHz, CDCl3) 20.80, 32.05 (d, J=22.1 Hz, CF2CH2-), 66.68 (-CH2O-

), 109-120 (m, CF3(CF2)6), 114.29, 120.20, 132.32, 155.20 (aromatic), 161.90 (PhCOOH). IR (cm-1) 3400-3020,

2970, 2890, 1694, 1606, 1516, 1431, 1322, 1206, 1176, 1145, 1026.

4-n-(7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluorododecyloxy)benzoic acid.

1H NMR (400 MHz, CDCl ) 8.03 (d, J=8.8 Hz, 2H), 6.91 (dd, J=8.8, 2H), 4.02 (t, J=6.2 Hz, 2H), 1.99-
3

2.15 (m, 2H), 1.78-1.86 (m, 2H), 1.61-1.68 (m, 2H), 1.44-1.55 (m, 4H). 13C NMR (400 MHz, CDCl3)

20.05, 25.73, 28.82, 30.80, 31.50 (d, J=22.1 Hz, CF2CH2-), 67.94 (-CH2O-), 111-120 (m, CF3(CF2)5),

114.18, 118.0, 132.36, 158.50 (aromatic), 171.50 (PhCOOH). IR (cm-1) 3390-3020, 2970, 2870, 1673,

1606, 1514, 1428, 1262, 1184, 1144, 1072.

4-n-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12.12-heptadecafluorododecyloxy)benzoic acid.

1H NMR (400 MHz, CDCl ) 8.04 (dd, J=9.2, 2.4 Hz, 2H), 6.94 (dd, J=9.2, 2.4 Hz, 2H), 4.09 (t, J=6.0 Hz, 2H),
3

13
2.13-2.26 (m, 2H), 1.82-1.97 (m, 4H). C NMR (400 MHz, CDCl3) 25.30, 28.75, 33.55 (d, JC-F=22.1 Hz,

CF2CH2), 67.53 (-CH2O-), 110-120 (m, CF3(CF2)7), 114.28, 121.30, 132.28, 154.10 (aromatic), 170.80

(PhCOOH). IR (cm-1) 3380-3010, 2980, 2880, 1690, 1606, 1515, 1255, 1147, 956.

Synthesis of 4-(n-alkyloxy)benzoyl hydrazides.[7] The preparation of 4-(n-nonyloxy)benzoyl

hydrazide is provided as a general example: A mixture of methyl p- (n-nonyloxy)benzoate (25.31 g,

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0.09 mol) and an excess of a solution of hydrazine monohydrate, NH2NH2.H2O (10.43 g, 0.21 mol) in

40.0 ml of ethanol was refluxed for 12h. The reaction was monitored by TLC. After the reaction was

complete, the mixture was cooled to room temperature and the white solid obtained was filtered off

and washed with water. The product was collected by vacuum filtration, recrystallized from

methanol/water and dried in the oven at 60°C.

4-(n-nonyloxy)benzoyl hydrazine, 27a.

Yield = 96%, mp = 99.6 °C. 1H NMR (400 MHz, CDCl3) 8.75 (s, br, 2H), 8.13 (s, br, 1H), 7.69 (d, J=12.0 Hz,

2H), 6.88 (d, J=12.0 Hz, 2H), 3.96 (t, J=6.4 Hz, 2H), 1.77 (q, J=6.8 Hz, 2H), 1.40-1.45 (m, 2H), 1.21–1.35 (m,

10H), 0.88 (t, J=6.8 Hz, 3H). 13C NMR (400 MHz, CDCl3) 14.10, 22.66, 25.97, 29.11, 29.24, 29.36, 29.50, 31.86,

68.22, 114.39, 124.60, 128.65, 162.09, 168.42. IR (cm-1) 3335, 2917, 2852, 1644, 1616, 1576, 1504, 1303, 1252,

980.

4-(n-decyloxy)benzoyl hydrazine, 27b.

Yield = 88%, mp = 101.2 °C. 1H NMR (400 MHz, CDCl3) 8.79 (s, br, 2H), 8.15 (s, br, 1H), 7.69 (d,

J=8.8 Hz, 2H), 6.83 (dd, J=9.2, 2.4 Hz, 2H), 3.91 (t, J=6.4 Hz, 2H), 1.69-1.77 (m, 2H), 1.37-1.41 (m,

2H), 1.15––1.30 (m, 12H), 0.88 (t, J=6.8 Hz, 3H). 13C NMR (400 MHz, CDCl3) 14.11, 22.66, 25.50,

25.97, 29.11, 29.30, 29.36, 29.54, 31.87, 68.17, 114.25, 124.67, 128.74, 161.99, 168.10. IR (cm-1)

3380, 2905, 2848, 1720, 1636, 1607, 1500, 1368, 1307, 1261, 1179, 1028.

4-(n-dodecyloxy)benzoyl hydrazine, 27c.

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Yield = 79%, mp = 102.9 °C. 1H NMR (400 MHz, CDCl3) 8.81 (s, br, 2H), 8.17 (s, br, 1H), 7.70 (d, J=8.0 Hz,

2H), 6.86 (d, J=8.4 Hz, 2H), 3.94 (t, J=6.4 Hz, 2H), 1.74-1.78 (m, 2H), 1.41-1.44 (m, 2H), 1.21––1.30 (m, 16H),

0.86 (t, J=6.8 Hz, 3H). 13C NMR (400 MHz, CDCl3) 14.11, 22.68, 25.99, 29.13, 29.35, 29.38, 29.56, 29.59,

29.63, 29.66, 31.91, 68.21, 114.37, 124.54, 128.73, 162.12, 168.37. IR (cm-1) 3330, 2916, 2852, 1646,1621, 1577,

1507, 1478, 1352, 1304, 1251, 1114, 1048, 982.

Synthesis of 4-(n-fluoroalkyloxybenzoyl) hydrazines.[8,9] The preparation of is provided as a

general example: A solution of 4-n-(7,7,8,8,9,9,10,10,10- nonafluorodecyloxy)benzoic acid (0.90 g,

2.04 mmol) in methanol (5.0 ml) containing a few drops of concentrated sulfuric acid was refluxed

for 12 h. Hydrazine monohydrate (0.51 g, 10.22 mmol) was added and the reflux was continued for 8

h. The reaction was monitored by TLC. Excess methanol was removed under reduced pressure and

the reaction mixture was poured into ice cold water. The crude product obtained was recrystallized

from methanol/water and dried in the oven at 60°C.

4-n-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyloxy)benzoyl hydrazine, 27d.

Yield = 48%. 1H NMR (400 MHz, CDCl3) 9.02 (s, br, 2H), 8.38 (s, br, 1H), 7.84 (d, J=8.8 Hz, 2H),
13
6.95 (d, J=5.2, 2H), 4.12 (t, J=6.0 Hz, 2H), 2.27-2.40 (m, 2H), 2.15-2.19 (m, 2H). C NMR (400

MHz, CDCl3) 19.74, 35.30 (d, J=22.4 Hz, CF2CH2-), 67.00 (- CH2O-), 110-120 (m, CF3(CF2)7),

114.64, 128.40, 129.09, 162.10 (aromatic), 168.90 (PhCONHNH2). IR (cm-1) 3190, 2940, 2860,

1611, 1593, 1564, 1453, 1254, 1192, 1141,1030.

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4-n-(7,7,8,8,9,9,10,10,10-nonafluorodecyloxy)benzoyl hydrazine, 27e.

Yield = 73%. 1H NMR (400 MHz, CDCl3) 8.96 (s, br,2H), 8.31 (s, br, 1H), 7.68 (d, J=8.8 Hz, 2H), 6.89 (d, J=8.8,
13
2H), 3.98 (t, J=6.4 Hz, 2H), 1.98-2.13 (m, 2H), 1.75-1.84 (m, 2H), 1.59-1.66 (m, 2H), 1.41-1.53 (m, 4H). C

NMR (400 MHz, CDCl3) 20.06, 25.73, 28.82, 28.88, 30.70 (d, J=22.4 Hz, CF2CH2-), 67.88 (-CH2O-), 110-120

(m, CF3(CF2)3), 114.41, 124.74, 128.64, 161.99 (aromatic), 168.34 (PhCONHNH2). IR (cm-1) 3269, 2944, 2869,

1605, 1504, 1223, 1172, 1130, 1006.

4-n-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-pentadecafluorodecyloxy)benzoyl hydrazine, 27f.

Yield = 60%. 1H NMR (400 MHz, CDCl3) 9.15 (s, br, 1H), 8.51 (s, br 1H), 8.06 (d, J=8.8 Hz, 2H), 6.94 (d, J=8.8

Hz, 2H), 4.12 (t, J=6.0 Hz, 2H), 2.28-2.40 (m, 2H), 2.10- 2.19 (m, 2H). 13C NMR (400 MHz, CDCl3) 20.62, 28.00

(d, J=22.4 Hz, CF2CH2-) 6.63 (-CH2O-), 110-120 (m, CF3(CF2)6), 114.24, 128.90, 132.33, 157.50 (aromatic),

170.10 (PhCONHNH2). IR (cm-1) 3270, 2941, 2862, 1610, 1506, 1253, 1178, 1135, 1023.

4-n-(7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluorododecyloxy)benzoyl hydrazine, 27g.

Yield = 74%. 1H NMR (400 MHz, CDCl3) 8.98 (s, br, 2H), 8.33 (s, br, 1H), 7.70 (dd, J=6.8, 2.0 Hz,

2H), 6.92 (dd, J=6.8, 2.0 Hz, 2H), 4.00 (t, J=6.2 Hz, 2H), 2.01-2.15 (m, 2H), 1.79-1.86 (m, 2H), 1.61-

1.69 (m, 2H), 1.44-1.52 (m, 4H). 13C NMR (400 MHz, CDCl3) 20.10, 26.00, 28.75, 28.90 31.50 (d,

J=22.4 Hz, CF2CH2-), 68.20 (-CH2O-), 110-120 (m, CF3(CF2)5), 114.43, 124.10, 128.63, 163.50

(aromatic), 166.50 (PhCONHNH2). IR (cm-1) 3275, 2948, 2869, 1605, 1505, 1249, 1186, 1140, 1048.

4n-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12heptadecafluorododecyloxy)-benzoyl hydrazine,
S 11
27h.

Yield = 71%. 1H NMR (400 MHz, CDCl3) 8.97 (s, br, 2H), 8.32 (s, br, 1H), 7.69 (d, J=8.8 Hz, 2H),

6.90 (d, J=8.4 Hz, 2H), 4.02 (t, J=5.6 Hz, 2H), 2.08-2.22 (m, 2H), 1.78- 1.92 (m, 4H). 13C NMR (400

MHz, CDCl3) 17.5, 20.4, 28.8 (d, J=22.4 Hz, CF2CH2-), 67.7 (-CH2O-), 110-120 (m, CF3(CF2)7),

114.51, 125.80, 128.62, 163.9 (aromatic), 174.3 (PhCONHNH2). IR (cm-1) 3273, 2947, 2880, 1589,

1504, 1251, 1198, 1144, 1013, 844.

Synthesis of N,N’-bis(4-n-alkyloxy)benzoyl hydrazines, or N-[4-(n- nonyloxybenzoyl)]-N’-[4-(n-

fluoroalkyloxybenzoyl)] hydrazines, or N,N’-bis(4- n-fluoroalkyloxy)benzoyl

hydrazines.[8,10,11]

The preparation of N,N’-bis(4-n-nonyloxy)benzoyl hydrazine is provided as a general example: A

mixture of 4-(n- nonyloxy)benzoic acid (0.40 g, 1.52 mmol) and oxalyl chloride (0.96 g, 7.60 mmol)

was heated at 40ºC in methylene chloride (3.0 ml) for 8 h. Excess oxalyl chloride was evaporated and

the residue was mixed with respected benzoyl hydrazine (0.39 g, 1.42 mmol) in dichloromethane

(15.0 ml). Triethylamine (0.2 ml, 1.42 mmol) was added and the mixture stirred at room temperature.

The reaction was monitored by TLC. The crude product was collected by filtration, recrystallized

from methanol/water and dried in the oven at 60°C.

N,N’-bis(4-n-nonyloxy)benzoyl hydrazine, 26a.

Yield = 51%. 1H NMR (400 MHz, CDCl3) 9.20 (s, 2H), 7.81 (d, J=8.8 Hz, 4H), 6.92 (d, J=8.8 Hz, 4H), 3.99 (t,
13
J=6.6 Hz, 4H), 1.75-1.82 (m, 4H), 1.41-1.49 (m, 4H), 1.22––1.38 (m, 20H), 0.89 (t, J=6.8 Hz, 6H). C NMR

(CDCl3) 14.12, 22.68, 25.99, 29.12, 29.26, 29.38, 29.52, 31.88, 68.29, 114.52, 123.33, 129.05, 162.56, 163.71.

S 12
IR (cm-1) 3271, 2917, 2848, 1684, 1604, 1540, 1465, 1434, 1308, 1295, 1254, 1174, 844, 771.

N-(4-n-nonyloxybenzoyl)-N’-(4-n-decyloxybenzoyl) hydrazine, 26b.

Yield = 72%. 1H NMR (400 MHz, CDCl3) 9.21 (s, br, 2H), 7.80 (d, J=8.4 Hz, 4H), 6.91 (d, J=8.4 Hz,

4H), 3.99 (t, J=6.6 Hz, 4H), 1.75-1.83 (m, 4H), 1.41-1.50 (m, 4H), 1.25-1.37 (m, 22H), ), 0.88 (t, J=6.6

Hz, 6H). 13C NMR (CDCl3) 13.97 (2C), 22.60 (2C), 25.96 (2C), 29.11 (2C), 29.18 (2C), 29.24 (2C),

29.31 (2C), 29.49 (1C), 31.82 (2C), 68.33 (2C), 114.56 (2C), 123.52 (2C), 129.04 (2C), 162.58 (2C),

163.80 (2C). IR (cm-1) 3224, 2954, 2919, 2851, 1639, 1605, 1577, 1508, 1454, 1248, 1174, 1016.

N-(4-n-nonyloxybenzoyl)-N’-(4-n-dodecyloxybenzoyl) hydrazine, 26c.

Yield = 69%. 1H NMR (400 MHz, CDCl3) 9.36 (s, br, 2H), 7.82 (d, J=8.8 Hz, 4H), 6.91 (d, J=7.6 Hz,

4H), 3.99 (t, J=6.6 Hz, 4H), 1.76-1.84 (m, 4H), 1.41-1.51 (m, 4H), 1.24-1.38 (m, 26H), ), 0.88 (t, J=6.8

Hz, 6H). 13C NMR (CDCl3) 14.08 (2C), 22.66 (2C), 25.99 (2C), 29.12 (2C), 29.24 (2C), 29.37 (2C),

29.51 (2C), 29.59 (2C), 29.63 (1C), 31.86 (1C), 31.91 (1C), 68.28 (2C), 114.47 (2C), 123.42 (2C),

129.10 (2C), 162.51 (2C),168.90 (2C). IR (cm-1) 3220, 2920, 2849, 1609, 1597, 1566, 1456, 1251,

1177, 1108, 1033.

N-[4-n-(nonyloxybenzoyl)]-N’-[4-n-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyloxybenzoyl)] hydrazine,

26d.[8]

Yield = 55%. 1H NMR (400 MHz, CDCl3) 9.55 (s, br, 1H), 9.46 (s, br, 1H), 7.83 (t, J=8.6 Hz, 4H),

6.90 (d, J=8.8 Hz, 4H), 4.08 (t, J=6.0 Hz, 2H), 3.98 (t, J=6.6 Hz, 2H), 2.24-2.40 (m, 2H), 2.08-2.17

S 13
 13
(m, 2H), 1.74-1.85 (m, 2H), 1.41-1.49 (m, 2H), 1.22-1.37 (m, 10H), ), 0.88 (t, J=6.6 Hz, 3H). C

NMR (CDCl3) 14.10, 20.51, 22.67, 25.99, 29.26 (2C), 29.38, 29.52 (2C), 31.88 (d, J=22.4 Hz,

CF2CH2-), 66.50, 68.28 (-CH2O-), 110-120 (m, CF3(CF2)8), 114.38, 114.46, 123.24, 124.02, 129.19,

129.30, 161.81, 162.58 (aromatic, 8C), 163.99, 164.22 (-CONH-). IR (cm-1) 3320, 2961, 2855, 1731,

1687, 1642, 1511, 1255, 1185, 1141, 1069.

N-[4-n-(nonyloxybenzoyl)]-N’-[4-n-(7,7,8,8,9,9,10,10,10-nonafluoro-decyloxybenzoyl)]

hydrazine, 26e.

Yield = 86%. 1H NMR (400 MHz, CDCl3) 9.10 (s, br, 2H), 7.81 (dd, J=8.8, 2.4 Hz, 4H), 6.93 (dd,

J=9.0, 1.0 Hz, 4H), 4.01 (m, 4H), 2.00-2.14 (m, 2H), 1.75-1.85 (m, 4H), 1.61-1.68 (m, 2H), 1.41-

1.53 (m, 6H), 1.24-1.37 (m, 10H), ), 0.87 (t, J=6.8 Hz, 3H). 13C NMR (CDCl3) 14.17, 20.08, 22.69,

25.73, 26.00, 28.83, 28.87, 29.12, 29.26, 29.37, 29.53, 31.89, 32.00 (d, J22.4 Hz, CF2CH2-), 67.94,

68.30 (-CH2O-), 110-120 (m, CF3(CF2)3), 114.51, 114.55, 126.20 (2C), 129.01, 129.05, 162.00,

162.80 (aromatic, 8C), 165.50, 166.30 (-CONH-). IR (cm-1) 3244. 3056, 2925, 2852, 1684, 1642,

1611, 1530, 1288, 1251, 1222, 1132, 920.

N-[4-n-(nonyloxybenzoyl)]-N’-[4-n-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-pentadecafluorodecyloxybenzoyl)]

hydrazine, 26f.

Yield = 69%. 1H NMR (400 MHz, CDCl3) 9.36 (d, J=6.4 Hz, 1H), 9.28 (d, J=6.0 Hz, 1H), 7.82 (t,

J=8.8 Hz, 4H), 6.91 (dd, J=8.8, 1.2 Hz, 4H), 4.08 (t, J=5.8 Hz, 2H), 3.98 (t, J=6.6 Hz, 2H), 2.23-2.40

(m, 2H), 2.08-2.17 (m, 2H), 1.74-1.84 (m, 2H), 1.40-1.49 (m, 2H), 1.23-1.36 (m, 10H), ), 0.87 (t,

J=7.0 Hz, 3H). 13C NMR (400 MHz, CDCl3) 14.11, 20.47, 22.68, 25.99, 27.90, 29.11, 29.26, 29.38,

S 14
29.52, 31.87 (d, J=22.4 Hz, CF2CH2-), 66.51, 68.29 (-CH2O-), 109-120 (m, CF3(CF2)6), 114.42,

114.50, 123.28, 124.05, 129.10, 129.21, 161.81, 162.58 (aromatic, 8C), 163.71, 163.93 (-CONH-).

IR (cm-1) 3294, 3248, 2922, 2853, 1686, 1642, 1612, 1510, 1195, 1142, 1017, 837.

N-[4-n-(nonyloxybenzoyl)]-N’-[4-n-(7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluorododecyloxybenzoyl)]

hydrazine, 26g.

Yield = 98%. 1H NMR (400 MHz, CDCl3) 9.37 (s, br, 2H), 7.82 (d, J=6.8 Hz, 4H), 6.91 (d, J=8.0 Hz,

4H), 4.00 (dd, J=6.4, 6.0 Hz, 4H), 2.01-2.16 (m, 2H), 1.75-1.88 (m, 4H), 1.61-1.71 (m, 2H), 1.42-1.57
13
(m, 6H), 1.25-1.36 (m, 10H), ), 0.89 (t, J=7.0 Hz, 3H). C NMR (400 MHz, CDCl3) 14.11, 20.10,

22.68, 25.75 (2C), 25.99, 28.85, 29.12, 29.26, 29.38, 29.52, 30.60, 31.88 (d, J=22.4 Hz, CF2CH2-),

67.93, 68.28 (-CH2O-), 109-120 (m, CF3(CF2)5), 114.43, 114.47, 123.50, 123.52, 129.13, 129.15,

162.36, 162.54 (aromatic, 8C), 163.80, 164.0 (-CONH-). IR (cm-1) 3210, 2930, 2840, 1737, 1642,

1611, 1530, 1509, 1380, 1233, 1217, 1143.

N-[4-n-(nonyloxybenzoyl)]-N’-[4-n-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,1-

heptadecafluorododecyloxybenzoyl)] hydrazine, 26h.

Yield = 69%. 1H NMR (400 MHz, CDCl3) 9.13 (dd, J=14.8, 6.0 Hz, 2H), 7.83 (dd, J=8.6, 5.4 Hz, 4H),

6.94 (d, J=8.8 Hz, 4H), 4.06 (t, J=5.8 Hz, 2H), 4.01 (t, J=6.6 Hz, 2H), 2.12-2.25 (m, 2H), 1.76-1.97 (m,

6H), 1.42-1.51 (m, 2H), 1.26-1.40 (m, 10H), ), 0.89 (t, J=6.6 Hz, 3H). 13C NMR (400 MHz, CDCl3)

14.08, 17.30, 22.67, 25.97, 28.60, 29.11, 29.27, 29.35, 29.50, 30.21, 31.86 (d, J=22.4 Hz, CF2CH2-),

67.45, 68.60 (-CH2O-), 110-120 (m, CF3(CF2)7), 114.49, 114.51, 123.40, 123.90, 129.04, 129.11,

167.10, 167.30 (aromatic, 8C), 169.20, 169.50 (-CONH-). IR (cm-1) 3280, 2920, 2851, 1667, 1613,

S 15
1573, 1476, 1461, 1261, 1188, 1146.

N,N’-bis[4-n-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyloxybenzoyl)] hydrazine, 28a.

Yield = 72%. 1H NMR (400 MHz, CDCl3) 8.99 (d, J=4.4 Hz, 2H), 7.84 (dd, J=6.8, 2.0 Hz, 4H), 6.97

(d, J=8.8 Hz, 4H), 4.12 (t, J=6.0 Hz, 4H), 2.26-2.42 (m, 4H), 2.10-2.22 (m, 4H). 13C NMR (400 MHz,

CDCl3) 28.00, 30.40 (d, J=22.4 Hz, CF2CH2), 66.70 (- CH2O-), 110-120 (m, CF3(CF2)5), 114.63,

127.50, 129.08, 138.10 (aromatic, 4C), 162.10 (-CONH-). IR (cm-1) 3200, 2954, 2891, 1610, 1594,

1518, 1470, 1455, 1243, 1191, 1140, 1043.

N,N’-bis[4-n-(7,7,8,8,9,9,10,10,10-nonafluorodecyloxybenzoyl)] hydrazine, 28b.

Yield = 77%. 1H NMR (400 MHz, CDCl3) 9.19 (s, br, 2H), 7.83 (d, J=8.8 Hz, 4H), 6.94 (d, J=8.0 Hz,

4H), 4.06 (t, J=10.8 Hz, 4H), 2.01-2.17 (m, 4H), 1.79-1.88 (m, 4H), 1.63-1.71 (m, 8H), 1.44-1.56 (m,

4H). 13C NMR (400 MHz, CDCl3) 20.05, 20.10, 25.73, 28.83, 30.71 (d, J=22.4 Hz, CF2CH2-), 67.94

(-CH2O-), 110-120 (m, CF3(CF2)3), 114.50, 118.05, 129.07, 163.80 (aromatic), 172.70 (-CONH-). IR

(cm1) 3251, 2944, 2871, 1609, 1572, 1461, 1219, 1187, 1130.

N,N’-bis[4-n-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-pentadecafluorodecyloxy-benzoyl)]

hydrazine, 28c.

Yield = 68%. 1H NMR (400 MHz, CDCl3) 9.12 (s, br, 2H), 7.69 (d, J=12.0 Hz, 4H), 6.88 (d, J=12.0

S 16
Hz, 4H), 3.96 (t, J=6.4 Hz, 4H), 2.26-2.41 (m, 4H), 2.11-2.19 (m, 4H).13C NMR (400 MHz, CDCl3)

20.80, 28.10 (d, J=22.4 Hz, CF2CH2-), 66.64 (-CH2O-), 110-120 (m, CF3(CF2)6), 114.25, 129.50,

132.34, 139.10 (aromatic), 162.20 (-CONH-). IR (cm-1) 3260, 2921, 2851, 1686, 1642, 1614, 1580,

1511, 1256, 1196, 1022.

N,N’-bis[4-n-(7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluorododecyloxybenzoyl)] hydrazine, 28d.

Yield =18%. 1H NMR (400 MHz, CDCl3) 9.15 (s, br, 2H), 8.04 (d, J=8.8 Hz, 4H), 7.84 (d, J=8.8 Hz,

4H), 6.94 (t, J=8.6 Hz, 4H), 4.02-4.07 (m, 4H), 2.01-2.18 (m, 4H), 1.79-1.89 (m, 4H), 1.62-1.72 (m,

4H), 1.45-1.60 (m, 4H). 13C NMR (400 MHz, CDCl3) 20.12, 25.64, 28.76, 28.83, 30.99 (d, J=22.4 Hz,

CF2CH2-), 68.02 (-CH2O-), 110-120 (m, CF3(CF2)5), 114.64, 129.06, 132.22, 162.52 (aromatic),

171.50 (-CONH-). IR (cm-1) 3270, 2920, 2850, 1607, 1575, 1440, 1240, 1176, 1136, 1030.

N,N’-bis[4-n-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyloxybenzoyl)] hydrazine, 28e.

Yield = 38%. 1H NMR (400 MHz, CDCl3) 9.16 (s, br, 2H), 8.04 (d, J=8.8 Hz, 4H), 7.72 (d, J=9.2 Hz,

4H), 6.93 (d, J=8.8 Hz, 4H), 4.04-4.09 (m, 4H), 2.11-2.25 (m, 4H), 1.81- 1.95 (m, 4H). 13C NMR (400

MHz, CDCl3) 17.28, 28.59, 30.67 (d, J=22.4 Hz, CF2CH2-), 67.38 (-CH2O-), 110-120 (m, CF3(CF2)7),

114.42, 129.34, 132.28, 161.75 (aromatic)168.27 (-CONH-). IR (cm-1) 3270, 2920, 2850, 1607, 1575,

1440, 1240, 1176, 1136, 1030.

2-Fluoro-4-(n-dodecyloxy)benzonitrile.[8]

S 17
2-Fluoro-4-hydroxybenzonitrile (6.00 g, 43.76 mmol) and potassium carbonate (15.12 g, 109.40 mmol) were

mixed with 70.0 ml of DMF under a nitrogen atmosphere. Next, 1- bromododecane (13.09 g, 52.51 mmol) was

added and the mixture was refluxed and monitored by TLC. After 48 h, the reaction mixture was cooled to room

temperature and poured into 300 ml of ice water. After acidification, the product was collected by vacuum

filtration and dried. Purification using silica chromatography (10% ethyl acetate in hexane) afforded the product

as a white solid. Yield = 8.62 g (64%). mp = 47.2 °C. 1H NMR (400 MHz, CDCl3) 7.47 (t, J=8.0 Hz, 1H), 6.73

(dd, J=8.8, 2.4 Hz, 1H), 6.67 (dd, J=11.0, 2.2 Hz, 1H), 3.97 (t, J=6.4 Hz, 2H), 1.74-1.82 (m, 2H), 1.39-1.47 (m,

2H), 1.22–– 1.32 (m, 16H), 0.86 (t, J=7.0 Hz, 3H). 13C NMR (CDCl3) 14.11, 22.70, 25.86, 28.82, 29.28, 29.36,

29.53, 29.58 (2C), 29.65, 31.93, 69.07 (-CH2O-), 102.62 (d, J=92.0 Hz), 111.68 (d, J=8.0 Hz), 114.49 (-CN),

134.10 (d, J=8.0 Hz), 163.32, 164.42 (d, J=44.0 Hz,), 165.88 (=C-O-, Ar). IR (cm-1) 2916, 2852, 2232, 1621,

1507, 1472, 1305, 1172, 1112.

2-Fluoro-4-(n-dodecyloxy)benzoic acid, 30.[8]

A solution of 2-fluoro-4-(n-dodecyloxy)benzonitrile (5.57 g, 18.26 mmol), concentrated sulfuric acid

(6.0 ml), water (6.0 ml) and acetic acid (60.0 ml) was refluxed. The reaction was monitored by TLC.

After 72 h, the solution was cooled and poured onto water (200 ml). The resulting precipitate was

filtered off, washed with water. The product was recrystallized from methanol/water and dried in the

oven at 60°C. Yield = 4.73 g (80%).1H NMR (400 MHz, CDCl3) 10.98 (s, br, 1H), 7.96 (t, J=8.6 Hz,

1H), 6.72 (dd, J=9.0, 2.6 Hz, 1H), 6.63 (dd, J=12.8, 2.4 Hz, 1H), 3.99 (t, J=6.4 Hz, 2H), 1.74-1.83 (m,

2H), 1.40-1.48 (m, 2H), 1.23––1.34 (m, 16H), 0.87 (t, J=6.8 Hz, 3H). 13C NMR (CDCl3) 14.13, 22.70,

25.91, 28.92, 29.14, 29.32, 29.36, 29.54, 29.58, 29.65, 31.93, 68.82 (-CH2O-), 102.77 (d, J=104.0 Hz),

110.82 (2C), 134.06, 162.98, 165.10 (d, J=44.0 Hz), 165.58 (-COOH). IR (cm-1) 3300-2500 (O-H

stretch), 2917, 2851, 1682, 1618, 1592, 1469, 1285, 1136, 1101.

S 18
2-Fluoro-4-(n-dodecyloxybenzoyl) hydrazine, 29.[8]

A solution of 2-fluoro-4-(n-dodecyloxy)benzoic acid (0.20 g, 0.62 mmol) in methanol (5.0 ml)

containing few drops of concentrated sulfuric acid was refluxed for 8 h. Hydrazine monohydrate (0.06

g, 0.06 ml, 1.85 mmol) was added and the reaction was continued to reflux for 10 h. The reaction was

monitored by TLC. Excess methanol was removed under reduced pressure and the reaction mixture

was poured into ice cold water. The crude material obtained was recrystallized from ethanol/water and

dried in the oven at 60°C to give the expected product as a white solid. Yield = 0.14 g (74%) 1H NMR

(400 MHz, CDCl3) 9.64 (d, J=10.4 Hz, 1H), 8.07 (t, J=9.0 Hz, 1H), 6.81 (dd, J=9.4, 2.2 Hz, 1H), 6.67

(dd, J=14.0, 2.4 Hz, 1H), 5.35 (s, br, 2H), 4.00 (t, J=6.6 Hz, 2H), 1.76-1.85 (m, 2H), 1.42-1.50 (m,

2H), 1.25-1.35 (m, 16H), 0.88 (t, J=6.8 Hz, 3H). 13C NMR (CDCl3) 14.13, 22.70, 25.92, 28.94, 29.32,

29.35, 29.54, 29.58, 29.64, 29.65, 31.92, 68.85 (-CH2O-), 102.04 (d, J=112.0 Hz), 111.54 (2C), 132.94,

158.99, 163.07, 164.00 (-CONH-). IR (cm-1) 3328, 2918, 2854, 1645, 1620, 1575, 1504, 1472, 1352,

1302, 1250, 1112, 1043.

N,N’-bis(4-dodecyloxy)benzoyl hydrazine, 33a.[8]

A mixture of 4-(n-dodecyloxy)benzoic acid (0.80 g, 2.61 mmol) and oxalyl chloride (1.66 g, 13.06

mmol) was heated at 40ºC in methylene chloride (4.0 ml) for 8 h. Excess oxalyl chloride was evaporated

and the residue was mixed with 4-(n-dodecyoxybenzoyl) hydrazine (0.79 g, 2.46 mmol) in

dichloromethane (15.0 ml). Triethylamine (0.34 ml, 2.46 mmol) was added and the mixture stirred at

room temperature. The reaction was monitored by TLC. After 8 h, it was precipitated and the crude

product was collected by filtration. The product was recrystallized from methanol/water and dried in

S 19
the oven at 60 °C. Yield = 0.58 g (40%). 1H NMR (400 MHz, CDCl3) 9.24 (s, 2H), 7.82 (d, J=8.8 Hz,

4H), 6.93 (d, J=8.8 Hz, 4H), 4.00 (t, J=6.6 Hz, 4H), 1.76-1.85 (m, 4H), 1.42-1.50 (m, 4H), 1.25-1.37
13
(m, 32H), 0.88 (t, J=6.8Hz, 6H). C NMR (CDCl3) 14.13, 22.70, 25.99,29.12, 29.36, 29.38, 29.57,

29.60, 29.64, 29.67, 31.93, 68.30 (-CH2O-), 114.52, 123.32, 129.06, 162.56 (aromatic), 163.60 (-

CONH-). IR (cm-1) 3212, 2919, 2850, 1597, 1566, 1456, 1248, 1174.

4-(dodecyloxybezoyl)-N’-(4-(dodecyloxy-2-fluorobenzoyl)hydrazine, 33b.[8]

A mixture of 2-fluoro-4-(n-dodecyloxy)benzoic acid, 5 (0.76 g, 2.34 mmol) and oxalyl chloride (1.49

g, 11.72 mmol) was heated at 40ºC in methylene chloride (5.0 ml) for 8 h. The excess of oxalyl

chloride was evaporated and the residue was mixed with 4-(n- dodecyoxybenzoyl) hydrazine (0.71 g,

2.22 mmol) in dichloromethane (14.0 ml). Triethylamine (0.31 ml, 2.22 mmol) was added and the

mixture stirred at room temperature. The reaction was monitored by TLC. After 8 h, the crude product

was collected by filtration, recrystallized from methanol/water and dried in the oven at 60°C. Yield =

0.90 g (65%). 1H NMR (400 MHz, CDCl3) 9.54 (s, 1H), 9.18 (s, 1H), 8.04 (t, J=9.0 Hz, 1H), 7.82 (d,

J=8.8 Hz, 2H), 6.94 (d, J=8.8 Hz, 2H), 6.81 (dd, J=2.4, 8.8 Hz, 1H), 6.67 (dd, J=2.4, 14.0 Hz, 1H),

4.01 (t, J=6.8 Hz, 4H), 1.76-1.85 (m, 4H), 1.42-1.51(m, 4H), 1.25-1.38 (m, 32H), 0.89 (t, J=6.8 Hz,

6H). 13C NMR (CDCl3) 14.00 (2C), 22.62 (2C), 25.89, 25.96, 28.94 (2C), 29.11 (2C), 29.28 (2C),

29.32 (2C), 29.48 (2C), 29.52 (2C), 29.58 (2C), 31.87 (2C), 68.33, 68.88, 102.09 (d, J=108.0 Hz),

110.52, 114.58 (2C), 123.48, 132.84, 129.02 (2C), 129.82, 132.84 (d, J=16.0 Hz), 159.46, 162.59,

163.16 (d, J=16.0 Hz), 163.93 (d, J=48.0 Hz). IR (cm-1) 3226, 2920, 2851, 1599, 1566, 1459, 1251,

1176, 1107.

N,N’-Bis(4-(dodecyloxy-2-fluorobenzoyl)hydrazine, 33c.[8]

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A mixture of 2-fluoro-4-(n-dodecyloxy)benzoic acid, 5 (0.50 g, 1.54 mmol) and oxalyl chloride (0.98 g, 7.71

mmol) was heated at 40ºC in methylene chloride (5.0 ml) for 8 h. The excess of oxalyl chloride was evaporated

and the residue was mixed with 2-fluoro-4- (n-dodecyloxybenzoyl) hydrazine, 6 (0.49 g, 1.46 mmol) in

dichloromethane (10.0 ml) Triethylamine (0.20 ml, 1.46 mmol) was added and the mixture stirred at room

temperature. The reaction was monitored by TLC. After 8 h, the crude product was collected by filtration,

recrystallized from methanol/water and dried in the oven at 60°C. Yield = 0.50 g (53%). 1H NMR (400 MHz,

CDCl3) 9.60 (d, J=9.6 Hz, 2H), 8.06 (t, J=9.0 Hz, 2H), 6.81 (dd, J=2.2, 9.0 Hz, 2H), 6.67(dd, J=2.0, 14.0 Hz,

2H), 4.01 (t, J=6.4 Hz, 4H), 1.76-1.86 (m, 4H), 1.42-1.52 (m, 4H), 1.26-1.39 (m, 32H), 0.89 (t, J=6.8 Hz, 6H).
13
C NMR (CDCl3) 14.13, 22.70, 25.92, 28.95, 29.32, 29.36, 29.54, 29.58, 29.65, 29.67, 31.93, 68.85 (-CH2O-),

102.04 (d, J=112.0 Hz), 110.32 (d, J=52.0 Hz), 111.54,132.92 (d, J=16.0 Hz), 158.98, 163.93 (d, J=48.0 Hz). IR

(cm-1) 3419, 2918, 2850, 1620, 1464, 1338, 1245, 1085.

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