Transition-metal-free N-arylation of tertiary amines using arynes

Abstract

The present invention relates to transition-metal-free process for the synthesis of tertiary arylamines comprises coupling reaction between arynes and N,N-dimethyl aniline compounds in presence of 18-crown-6, KF and THF.

Claims

1. A transition metal-free synthesis of tertiary arylamines compounds of general formula (I) ##STR00046## wherein ##STR00047## R.sup.1=ethyl, methyl or R.sup.2=H, alkyl (C.sub.1-C.sub.5), C.sub.6-C.sub.8-aryl, halogen (F, Cl, Br, I), C(O)(OCH.sub.3), C(O)(OCH.sub.2CH.sub.3), CHO, CN, OH, CHCHCOOEt, CHCHC.sub.6H.sub.4NO.sub.2, OCH.sub.3, OPh, ##STR00048## R.sup.3=H, CH3, halogen (F, Cl, Br, I), R.sup.4=H or D; or R.sup.2+R.sup.3=OCH2-O, CHCHCHCH; C(SO2Cl)=CHCHCH; comprising the steps of: i. mixing 2-trimethylsilylaryl trifluoromethyl sulphonate of formula (II) and tertiary amine compounds of formula (III) in the ratio ranging between 2:1 to 1:2 in presence of 18-crown-6, KF and solvent (THF) ##STR00049## wherein R.sup.1, R.sup.2 and R.sup.3 is as defined above.

2. The process according to claim 1, wherein the 2-trimethylsilylaryl trifluoromethyl sulphonate are selected from the group consisting of 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethanesulfonate, 4,5-difluoro-2-(trimethylsilyl)phenyl tri-fluoromethanesulfonate, 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 2-methoxy-6-(trimethylsilyl)phenyl trifluoromethanesulfonate, 2-(trimethylsilyl)-naphthalen-1-yl trifluoromethanesulfone, 4-methyl-2-(trimethylsilyl)-phenyl trifluoromethanesulfonate.

3. The process according to claim 1, wherein the tertiary amine compounds are selected from the group consisting of N, N-diethylaniline, N-methyl-N-phenylaniline, N,N-dimethylaniline, N,N,4-trimethylaniline, 3-(dimethylamino)phenol, 4-bromo-N,N-dimethylaniline, 4-iodo-N,N-dimethyl aniline, 4-(dimethyl amino) benzonitrile, ethyl 4-(dimethylamino)benzoate, 4-(dimethylamino) benzaldehyde, N,N,3-trimethylaniline, 3-bromo-N,N-dimethylaniline, methyl 2-(dimethylamino)benzoate, N,N,3,5-tetramethyl aniline, diethyl (4-(dimethylamino)benzyl)phosphonate (E)-N,N-dimethyl-4-(2-(thiophen-2-yl)vinyl)aniline, N,N-dimethyl-4-(phenyl ethynyl)aniline, N,N-dimethyl naphthalene-1-amine, 5-(dimethyl-amino) naphthalene-1-sulfonyl chloride, 4,4-(phenylmethylene)bis(N,N-dimethylaniline), ethyl (E)-3-(4-(dimethylamino)phenyl)acrylate, (E)-N,N-dimethyl-4-(4-nitrostyryl)-aniline, 5-(4-(dimethylamino)phenyl)thiophene-2-carbaldehyde, and 3-(dimethylamino)phenol.

4. The process according to claim 1, further comprises addition of 1.0 equiv ammonium bicarbonate (NH.sub.4HCO.sub.3) to increase the yield of tertiary arylamines.

5. The process according to claim 1, wherein the reaction is carried out at a temperature in the range of 58 to 62 C. for period in the range of 11 to 12 hours.

6. The process according to claim 1, wherein the coupling reaction is carried out under argon atmosphere.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 represents transition metal free process for the synthesis of tertiary arylamine of general formula I.

(2) FIG. 2 represents synthesis of N-methyl-N-phenylaniline as in example 1.

(3) FIG. 3 represents synthesis of N-methyl-N-phenylaniline as in example 2.

(4) FIG. 4 represents synthesis of N,N-dimethyl-N-(p-tolyl)benzo[d][1,3]dioxol-4-aminium salt as in example 3.

DETAILED DESCRIPTION OF INVENTION

(5) The present invention provides a transition metal free method for the synthesis of tertiary arylamine of general formula I by the reaction of arynes generated by 2-trimethylsilylaryl trifluoromethyl sulphonate of formula II with tertiary amine of formula III in excellent yields. One preferred tertiary amine is N,N-dimethyl aniline.

(6) Accordingly, present invention provides a transition metal-free process for the synthesis of tertiary arylamines compounds of general formula (I)

(7) ##STR00005##

(8) wherein R1=ethyl, methyl or;

(9) ##STR00006## R2=H, alkyl (C1-C5), aryl (phenyl, C6-C8), halogen (F, Cl, Br, I), esters (C2-C4), CHO, CN, OH, CHCHCOOEt, CHCHC6H4NO2, OCH3, OPh,

(10) ##STR00007## R3=H, CH.sub.3, halogen (F, Cl, Br, I), R4=H or D; or R2+R3=OCH2-O, CHCHCHCH; C(SO2Cl)CHCHCH; comprising the steps of: i. mixing aryne precursor 2-trimethylsilylaryl trifluoromethyl sulphonate of formula (II) and tertiary amines derivatives of formula (III) in presence of 18-crown-6, KF and solvent (THF) and optionally in the presence of a base at a temperature in the range of 58 to 62 C. preferably 60 C. under inert atmosphere for a period of 10-15 hrs preferably 12 hrs.

(11) ##STR00008##

(12) wherein R.sup.1, R.sup.2 and R.sup.3 is as defined above;

(13) The present invention provides a transition-metal-free synthesis of tertiary arylamines of general formula I further comprising of addition of ammonium bicarbonate (NH.sub.4HCO.sub.3) to increase the yield.

(14) The aryne precursors 2-trimethylsilylaryl trifluoromethyl sulphonate of formula (II) are selected from the group comprising 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethanesulfonate, 4,5-difluoro-2-(trimethylsilyl)phenyl tri-fluoromethanesulfonate, 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 2-methoxy-6-(trimethylsilyl)phenyl trifluoromethanesulfonate, 2-(trimethylsilyl)-naphthalen-1-yl trifluoromethanesulfonate, 4-methyl-2-(trimethylsilyl)-phenyl trifluoromethanesulfonate.

(15) The tertiary amines of Formula III are selected from the group comprising of N,N-diethylaniline, N,N-dimethylaniline, N,N,4-trimethylaniline, 3-(dimethylamino)phenol, 4-bromo-N,N-dimethylaniline, 4-iodo-N,N-dimethyl aniline, 4-(dimethylamino)benzonitrile, ethyl 4-(dimethylamino)benzoate, 4-(dimethylamino)benzaldehyde, N,N,3-trimethylaniline, 3-bromo-N,N-dimethylaniline, methyl 2-(dimethylamino)benzoate, N,N,3,5-tetramethyl aniline, diethyl (4-(dimethylamino)benzyl)phosphonate, (E)-N,N-dimethyl-4-(2-(thiophen-2-yl)vinyl)aniline, N,N-dimethyl-4-(phenylethynyl)aniline, N,N-dimethyl naphthalen-1-amine, 5-(dimethyl-amino)naphthalene-1-sulfonyl chloride, 4,4-(phenylmethylene)bis(N,N-dimethylaniline), ethyl (E)-3-(4-(dimethylamino)phenyl)acrylate, (E)-N,N-dimethyl-4-(4-nitrostyryl)-aniline, 5-(4-(dimethylamino)phenyl)thiophene-2-carbaldehyde, 3-(dimethylamino)phenol, 1,2,3,4-tetrahydroisoquinoline.

(16) The invention further demonstrates the optimization of reaction conditions and molar ratios of the reactants along with the yields and tabulated below in table 1 and table 2.

(17) ##STR00009##

(18) TABLE-US-00001 TABLE 1 equiv equiv Yield of 3 Sr. No. of 1 of 2 Conditions (%) 1 1.2 1 KF (2.4 equiv), 18-Crown-6 (2.4 equiv), THF (1.0 mL), 33 60 C., 12 h. 2 1.2 1 KF (2.4 equiv), 18-Crown-6 (2.4 equiv), NH.sub.4HCO.sub.3 88 (1.0 equiv), THF (1.0 mL), 40 C., 12 h. 3 1.2 1 KF (2.4 equiv), 18-Crown-6 (2.4 equiv), NH.sub.4HCO.sub.3 95 (1.0 equiv), THF (1.0 mL), 60 C., 12 h. 4 1.2 1 TBAF (2.4 equiv), THF (1.0 mL), 60 C., 12 h. 73 5 1.2 1 TBAF (2.4 equiv), NaHCO.sub.3 (1.0 equiv), 78 THF (1.0 mL), 60 C., 12 h. 6 1.2 1 TBAF (2.4 equiv), NH.sub.4HCO.sub.3 (1.0 equiv), 80 THF (1.0 mL), 60 C., 12 h. 7 1 1.2 TBAF (2.4 equiv), NH.sub.4HCO.sub.3 (1 equiv), 75 THF (1.0 mL), 60 C., 12 h. 8 1 1.2 CsF (2.4 equiv), CH.sub.3CN (1.0 mL), 60 C., 12 h 6

(19) TABLE-US-00002 TABLE 2 yield of 3 Entry variation from the standard conditions.sup.a (%).sup.b 1 None 33 2 CsF instead of KF and 18-crown-6, CH.sub.3CN as the 6 solvent 3 TBAF instead of KF and 18-crown-6 73.sup.c 4 (NH.sub.4)HCO.sub.3 1.0 equiv as a additive with TBAF 80.sup.c 5 (NH.sub.4)HCO.sub.3 1.0 equiv as a additive with KF and 98 (95).sup.d 18-crown-6 6 NaHCO.sub.3 1.0 equiv as a additive with KF and 67 18-crown-6 7 H.sub.2O 1.0 equiv as a additive with KF and 70 18-crown-6 8 Reaction temperature 40 C. instead of 60 C. with 88 (NH.sub.4)HCO.sub.31.0 equiv as a additive 9 Reaction time 6 h instead of 12 h with (NH.sub.4)HCO.sub.3 1.0 78 equiv as a additive .sup.aStandard conditions: 1 (0.25 mmol), 2 (0.30 mmol), KF (2.4 equiv), 18-crown-6 (2.4 equiv), THF (1.0 mL), 60 C. and 12 h. .sup.bThe yields were determined by .sup.1H NMR analysis of crude products using CH.sub.2Br.sub.2 as the internal standard. .sup.cIsolated yield at 0.25 mmol scale. .sup.dIsolated yield at 0.50 mmol scale in parentheses. As is evident from the above table, use of base facilitates the reaction and thus yield of the product (refer entry 1 and 2). It is further observed that the yield is higher at higher temperature when the other conditions are same (refer entry 2 and 3) and the appropriate molar ratio of compounds 1 and 2 observed to be in the range of 1:2 to 2:1 and product yield may vary in the range of 60-96%.

EXAMPLES

(20) The following examples are given by way of illustration and therefore should not be construed to limit the scope of the invention.

Example 1

Synthesis of N-methyl-N-phenylaniline (FIG. 2)

(21) ##STR00010##

(22) To a flame-dried screw-capped tube equipped with a magnetic stir bar were added 18-crown-6 (0.317 g, 1.2 mmol), KF (0.070 g, 1.2 mmol) and NH.sub.4HCO.sub.3 (0.040 g, 0.50, mmol). Then the screw-capped tube was evacuated and backfilled with argon. The mixture was dissolved in THF (2.0 mL) under argon atmosphere and then to the stirring solution were added the N, N-dimethylaniline 1 (0.061 g, 65 L, 0.50 mmol) and 2-(trimethylsilyl)phenyltrifluoro-methanesulfonate 2 (0.179 g, 146 L, 0.60 mmol) at room temperature (27 C.). Then the screw-capped tube kept in a preheated oil bath at 60 C. for 12 h. The reaction mixture cooled and the residue on column chromatography afforded N-methyl-N-phenylaniline 3 as a colourless oil (0.087 g, 95%).

(23) R.sub.f (Pet. ether/DCM=90/10): 0.66; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.28 (t, J=7.6 Hz, 4H), 7.03 (d, J=8.2 Hz, 4H), 6.96 (t, J=7.3 Hz, 2H), 3.32 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3): 149.18, 129.33, 121.39, 120.58, 40.38. HRMS (ESI) calculated [M+H].sup.+ for C.sub.13H.sub.14N: 184.1121. found: 184.1118. FTIR (cm.sup.1): 3036, 2929, 2879, 1591, 1496, 1342, 1271, 1253, 1186, 1156, 1131, 1092, 1074, 1029, 864, 750, 693.

Example 2

Synthesis of N-methyl-N-phenylaniline in the absence of NH4HCO3 (FIG. 3)

(24) ##STR00011##

(25) To a flame-dried screw-capped tube equipped with a magnetic stir bar were added N, N-dimethylaniline 1 (0.030 g, 32.0 L, 0.25 mmol) and 2-(trimethylsilyl)phenyltrifluoromethanesulfonate 2 (0.090 g, 73 L, 0.30 mmol). The mixture was dissolved in THF (1.0 mL) under argon atmosphere and then to the stirring solution was added the tetrabutyl ammonium fluoride (TBAF) (0.60 mL, 0.60 mmol) at room temperature (25 C.). Then the tube was kept in a preheated oil bath at 60 C. for 12 h. Usual processing of the reaction mixture followed by column chromatography of a crude reaction mixture afforded N-methyl-N-phenylaniline 3 as a colourless oil (0.033 g, 73%).

Example 3

Synthesis of N,N-dimethyl-N-(p-tolyl)benzo[d][1,3]dioxol-4-aminium salt (intermediate in this reaction) (FIG. 4)

(26) ##STR00012##

(27) To a flame-dried screw-capped tube equipped with a magnetic stir bar was added dry CsF (0.095 g, 0.60 mmol) and then CH.sub.3CN under argon atmosphere (1.0 mL). To the stirring solution N,N,4-trimethylaniline 4 (0.034 g, 37 L, 0.25 mmol) and 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethanesulfonate 5 (0.102 g, 0.3 mmol) were added at room temperature (27 C.). Then tube was kept in a preheated oil bath at 60 C. for 12 h. The reaction mixture cooled and the residue was purified by column chromatography to afford N,N-dimethyl-N-(p-tolypbenzo[d][1,3]dioxol-4-aminium salt 6 as a white solid. (0.100 g, 95%).

(28) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.40 (d, J=8.6 Hz, 2H), 7.29 (d, J=8.6 Hz, 2H), 7.18 (dd, J.sub.1=8.8 Hz, J.sub.2=2.6 Hz, 1H), 6.84 (d, J=8.8 Hz, 1H), 6.75 (d, J=2.6 Hz, 1H), 6.01 (s, 2H), 3.95 (s, 6H), 2.35 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.30, 149.14, 146.39, 142.56, 141.16, 131.18, 120.84, 114.84, 108.41, 103.02, 102.89, 58.99, 20.90. .sup.19F NMR (376 MHz, CDCl.sub.3) 78.41. HRMS (ESI) calculated [M].sup.+ for C.sub.16H.sub.18O.sub.2N: 256.1332. found: 256.1334. FTIR (cm.sup.1): 3504, 3114, 3059, 3016, 2919, 1615, 1508, 1488, 1383, 1263, 1226, 1159, 1125, 1112, 1031, 971, 927, 898, 819, 756, 639.

Example 4

Synthesis of N,4-Dimethyl-N-phenylaniline

(29) ##STR00013##

(30) Following the general procedure, treatment of N,N,4-trimethylaniline (0.068 g, 73 L, 0.50 mmol) with 2-(trimethylsilyl)phenyltrifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded N,4-dimethyl-N-phenylaniline as a colorless oil (0.091 g, 92%).

(31) R.sub.f (Pet. ether/DCM=90/10): 0.64; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.29-7.25 (m, 2H), 7.16 (d, J=8.1 Hz, 2H), 7.04 (d, J=8.4 Hz, 2H), 6.98-6.95 (m, 2H), 6.91 (t, J=7.3 Hz, 1H), 3.33 (s, 3H), 2.37 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.50, 146.73, 132.19, 130.05, 129.15, 122.69, 119.93, 118.33, 40.46, 20.88. HRMS (ESI) calculated [M+H].sup.+ for C.sub.14H.sub.16N: 198.1277. found: 198.1275. FTIR (cm.sup.1): 3059, 3027, 2923, 2870, 1597, 1572, 1512, 1497, 1342, 1296, 1268, 1254, 1187, 1131, 1089, 1067, 868, 822, 751, 696.

Example 5

Synthesis of 4-Bromo-N-methyl-N-phenylaniline

(32) ##STR00014##

(33) Following the general procedure, treatment of 4-bromo-N,N-dimethylaniline (0.100 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NR.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded 4-bromo-N-methyl-N-phenylaniline as a white solid (0.112 g, 85%).

(34) R.sub.f (Pet. ether/DCM=90/10): 0.62; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.34-7.29 (m, 4H), 7.07-7.01 (m, 3H), 6.84 (d, J=8.8 Hz, 2H), 3.29 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 148.67, 148.26, 132.07, 129.55, 122.71, 122.09, 120.71, 112.80, 40.42. HRMS (ESI) calculated [M+H].sup.+ for C.sub.13H.sub.13NBr: 262.0226. found: 262.0256. FTIR (cm.sup.1): 3062, 3037, 2926, 2882, 2815, 1583, 1489, 1454, 1343, 1254, 1185, 1133, 1119, 1075, 866, 815, 754, 734, 696 (CBr).

Example 6

Synthesis of 4-Iodo-N-methyl-N-phenylaniline

(35) ##STR00015##

(36) Following the general procedure, treatment of 4-iodo-N,N-dimethyl aniline (0.124 g, 0.50 mmol) with 2-(trimethylsilyl)phenyltrifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded 4-iodo-N-methyl-N-phenylaniline as a white solid (0.131 g, 85%).

(37) R.sub.f (Pet. ether/DCM=90/10): 0.64; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.50 (d, J=8.8 Hz, 2H), 7.32 (t, J=8.2 Hz, 2H), 7.10-7.04 (m, 3H), 6.72 (d, J=8.8 Hz, 2H), 3.29 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3): 148.85, 148.46, 137.95, 129.60, 123.13, 122.68, 120.66, 82.20, 40.34. HRMS (ESI) calculated [M+H].sup.+ for C.sub.13H.sub.13IN: 310.0092. found: 310.0100. FTIR (cm.sup.1): 3025, 2923, 2815, 1577, 1481, 1333, 1237, 1118, 1056, 805, 746, 687.

Example 7

Synthesis of 4-(Methyl (phenyl)amino)benzonitrile

(38) ##STR00016##

(39) Following the general procedure, treatment of 4-(dimethylamino)benzonitrile (0.073 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=98/01) afforded 4-(methyl(phenyl)amino)benzonitrile as a colorless oil (0.062 g, 60%).

(40) R.sub.f (Pet. ether/EtOAc=95/05): 0.60; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.46-7.42 (m, 4H), 7.30-7.21 (m, 3H), 6.74 (d, J=8.9 Hz, 2H), 3.36 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 152.04, 146.87, 133.35, 130.17, 126.56, 126.31, 120.48, 113.91, 99.40, 40.26. HRMS (ESI) calculated [M+H].sup.+ for C.sub.14H.sub.13N.sub.2: 209.1073. found: 209.1077. FTIR (cm.sup.1): 3061, 3039, 2946, 2886, 2215 (cyano group), 1609, 1591, 1513, 1494, 1355, 1257, 1176, 1142, 1119, 869, 823, 773, 701.

Example 8

Synthesis of Ethyl 4-(methyl (phenyl)amino)benzoate

(41) ##STR00017##

(42) Following the general procedure, treatment of ethyl 4-(dimethylamino)benzoate (0.097 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=99/01) afforded Ethyl 4-(methyl(phenyl)amino)benzoate as a colorless oil (0.110 g, 86%).

(43) R.sub.f (Pet. ether/EtOAc=95/05): 0.63; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (d, J=8.9 Hz, 2H), 7.39 (t, J=7.8 Hz, 2H), 7.22-7.18 (m, 3H), 6.77 (d, J=8.9 Hz, 2H), 4.33 (q, J=7.1 Hz, 2H), 3.36 (s, 3H), 1.36 (t, J=7.1 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 166.90, 152.57, 147.66, 131.06, 129.89, 125.89, 125.36, 119.67, 113.98, 60.41, 40.33, 14.57. HRMS (ESI) calculated [M+H].sup.+ for C.sub.16H.sub.18O.sub.2N: 256.1332. found: 256.1353. FTIR (cm.sup.1): 3061, 3038, 2980, 2820, 1705 (ester), 1609, 1591, 1567, 1515, 1495, 1351, 1314, 1276, 1181, 1107, 870, 840, 768, 730, 698.

Example 9

Synthesis of 4-(Methyl (phenyl)amino)benzaldehyde

(44) ##STR00018##

(45) Following the general procedure, treatment of 4-(dimethylamino)benzaldehyde (0.075 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NR.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=95/05) afforded 4-(methyl(phenyl)amino)benzaldehyde as a yellow solid (0.032 g, 30%).

(46) R.sub.f (Pet. ether/EtOAc=90/10): 0.37; .sup.1H NMR (400 MHz, CDCl.sub.3) 9.76 (s, 1H), 7.69 (d, J=8.9 Hz, 2H), 7.44 (t, J=7.8 Hz, 2H), 7.28-7.27 (m, 1H), 7.23 (d, J=7.8 Hz, 2H), 6.78 (d, J=8.9 Hz, 2H), 3.39 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 190.52, 153.88, 147.00, 131.78, 130.13, 126.79, 126.67, 126.33, 113.51, 40.43. HRMS (ESI) calculated [M+H].sup.+ for C.sub.14H.sub.14ON: 212.1070. found: 212.1074. FTIR (cm.sup.1): 3061, 3037, 2918, 2818, 2732, 1683, 1604, 1587, 1560, 1516, 1494, 1355, 1310, 1257, 1232, 1167, 1135, 1119, 1135, 1119, 1069, 1025, 872, 822, 769, 715, 699.

Example 10

Synthesis of N,3-Dimethyl-N-phenylaniline

(47) ##STR00019##

(48) Following the general procedure, treatment of N,N,3-trimethylaniline (0.068 g, 72 L, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded N,3-dimethyl-N-phenylaniline as a colorless oil (0.095 g, 96%).

(49) R.sub.f (Pet. ether/DCM=90/10): 0.64; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.30 (t, J=7.9 Hz, 2H), 7.20 (t, J=7.7 Hz, 1H), 7.04 (d, J=7.8 Hz, 2H), 6.97 (t, J=7.3 Hz, 1H), 6.89-6.87 (m, 2H), 6.83 (d, J=7.3 Hz, 1H), 3.34 (s, 3H), 2.34 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.27, 149.15, 139.14, 129.26, 129.16, 122.51, 121.60, 121.07, 120.24, 118.06, 40.40, 21.69. HRMS (ESI) calculated [M+H].sup.+ for C.sub.14H.sub.16N: 198.1277. found: 198.1277. FTIR (cm.sup.1): 3037, 2920, 2811, 1594, 1583, 1495, 1456, 1344, 1262, 1191, 1172, 1127, 1094, 1071, 1029, 993, 922, 806, 751, 693.

Example 11

Synthesis of 3-Bromo-N-methyl-N-phenylaniline

(50) ##STR00020##

(51) Following the general procedure, treatment of 3-bromo-N,N-dimethylaniline (0.100 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded 3-bromo-N-methyl-N-phenylaniline as a colorless oil (0.123 g, 94%).

(52) R.sub.f (Pet. ether/DCM=90/10): 0.63; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.37-7.33 (m, 2H), 7.13-7.06 (m, 5H), 6.99 (d, J=7.4 Hz, 1H), 6.84 (d, J=8.2 Hz, 1H), 3.31 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 150.54, 148.34, 130.35, 129.68, 123.60, 123.39, 123.15, 122.62, 120.54, 116.47, 40.39. HRMS (ESI) calculated [M+H].sup.+ for C.sub.13H.sub.13NBr: 262.0226. found: 262.0229. FTIR (cm.sup.1): 3402, 3062, 3037, 2927, 2814, 1586, 1560, 1495, 1481, 1343, 1247, 1133, 1101, 1081, 1070, 984, 887, 835, 760, 699 (CBr).

Example 12

Synthesis of Methyl 2-(methyl (phenyl)amino)benzoate

(53) ##STR00021##

(54) Following the general procedure, treatment of methyl 2-(dimethylamino)benzoate (0.090 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=99/01) afforded methyl 2-(methyl(phenyl)amino)benzoate as a yellow oil (0.079 g, 65%).

(55) R.sub.f (Pet. ether/EtOAc=95/05): 0.63; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.81 (d, J=7.7 Hz, 1H), 7.54 (t, J=7.9 Hz, 1H), 7.30-7.27 (m, 2H), 7.18-7.15 (m, 2H), 6.75 (t, J=7.2 Hz, 1H), 6.65 (d, J=7.9 Hz, 2H), 3.60 (s, 3H), 3.29 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 167.62, 149.38, 148.25, 133.36, 131.54, 129.44, 129.15, 129.01, 125.35, 118.11, 114.40, 52.15, 40.47. HRMS (ESI) calculated [M+H].sup.+ for C.sub.15H.sub.16O.sub.2N: 242.1176. found: 242.1176. FTIR (cm.sup.1): 3384, 3062, 3036, 2997, 2949, 2884, 2814, 1732 (ester), 1594, 1500, 1454, 1433, 1349, 1293, 1247, 1189, 1127, 1097, 1080, 1068, 991, 965, 871, 772, 749, 716, 693.

Example 13

Synthesis of N,3,5-trimethyl-N-phenylaniline

(56) ##STR00022##

(57) Following the general procedure, treatment of N,N,3,5-tetramethyl aniline (0.075 g, 82 L, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded N,3,5-trimethyl-N-phenylaniline as a colorless oil (0.086 g, 81%).

(58) R.sub.f (Pet. ether/DCM=90/10): 0.59; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.32-7.28 (m, 2H), 7.03 (d, J 7.7 Hz, 2H), 6.96 (t, J=7.4 Hz, 1H), 6.72 (s, 2H), 6.68 (s, 1H), 3.32 (s, 3H), 2.30 (s, 6H). .sup.13C NMR (100 MHz, CDCl.sub.3): 149.33, 149.12, 138.97, 129.22, 123.72, 120.83, 119.98, 119.01, 40.46, 21.57. HRMS (ESI) calculated [M+H].sup.+ for C.sub.15H.sub.18N: 212.1439. found: 212.1442. FTIR (cm.sup.1): 3035, 2917, 2869, 2811, 1591, 1497, 1379, 1349, 1289, 1259, 1205, 1130, 1097, 1030, 1005, 992, 934, 847, 824, 785, 751, 693.

Example 14

Synthesis of Diethyl (4-(methyl (phenyl)amino)benzyl)phosphonate

(59) ##STR00023##

(60) Following the general procedure, treatment of diethyl (4-(dimethylamino)benzyl)phosphonate (0.135 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=50/50) afforded diethyl (4-(methyl(phenyl)amino)benzyl)phosphonate as a yellow oil (0.144 g, 87%).

(61) R.sub.f (Pet. ether/EtOAc=40/60): 0.41; NMR (400 MHz, CDCl.sub.3) 7.29 (t, J=8.1 Hz, 2H), 7.22 (dd, J.sub.1=8.5 Hz, J.sub.2=2.4 Hz, 2H), 7.03 (d, J=7.8 Hz, 2H), 6.99-6.96 (m, 3H), 4.09-4.02 (m, 4H), 3.32 (s, 3H), 3.12 (d, J=21.3 Hz, 2H), 1.29 (t, 1=7.1, Hz, 6H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.06, 147.98 (d, J=3.26 Hz), 130.63 (d, J=6.65 Hz), 129.29, 123.97 (d, J=9.34 Hz), 121.47, 120.65, 120.48 (d, J=2.64 Hz), 62.21 (d, J=6.71 Hz), 40.34, 33.01 (d, J=139.1 Hz), 16.51 (d, J=5.91 Hz). HRMS (ESI) calculated [M+H].sup.+ for C.sub.18H.sub.25O.sub.3NP: 334.1567. found: 334.1562. FTIR (cm.sup.1): 3463, 3299, 3059, 3033, 2982, 2930, 2907, 2814, 1596, 1571, 1513, 1497, 1452, 1391, 1366, 1343, 1252 (PO), 1190, 1163, 1131, 1097, 1054, 1028, 962, 870, 850, 770, 754, 700.

Example 15

Synthesis of (E)-N-Methyl-N-phenyl-4-(2-(thiophen-2-yl)vinyl)aniline

(62) ##STR00024##

(63) Following the general procedure, treatment of (E)-N,N-dimethyl-4-(2-(thiophen-2-yl)vinyl)aniline (0.057 g, 0.25 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.089 g, 73 L, 0.30 mmol) in the presence of KF (0.034 g, 0.60 mmol), 18-crown-6 (0.158 g, 0.60 mmol) and (NH.sub.4)HCO.sub.3 (0.020 g, 0.25 mmol) in THF (1.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=90/10) afforded (E)-N-methyl-N-phenyl-4-(2-(thiophen-2-yl)vinyl)aniline as a yellow solid (0.067 g, 93%).

(64) R.sub.f (Pet. ether/DCM=80/20): 0.47; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.37 (d, J=8.6 Hz, 2H), 7.33 (t, J=7.9 Hz, 2H), 7.16 (d, J=4.8 Hz, 1H), 7.13-7.10 (m, 3H), 7.06-7.03 (m, 2H), 7.01-6.99 (m, 1H), 6.96 (d, J=8.6 Hz, 2H), 6.90 (d, J=16.1 Hz, 1H), 3.55 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 148.69, 148.58, 143.62, 129.48, 129.30, 128.32, 127.66, 127.32, 125.31, 123.69, 122.61, 122.26, 119.44, 118.95, 40.36. HRMS (ESI) calculated [M+H].sup.+ for C.sub.19H.sub.18NS: 292.1154. found: 292.1184. FTIR (cm.sup.1): 3018, 2925, 1593, 1519, 1494, 1344, 1248, 1183, 1156, 1134, 1114, 1085, 954, 942, 858, 826, 759, 726, 692, 583, 501.

Example 16

Synthesis of N-Methyl-N-phenyl-4-(phenylethynyl)aniline

(65) ##STR00025##

(66) Following the general procedure; treatment of N,N-dimethyl-4-(phenylethynyl)aniline (0.111 g, 0.50 mmol) with 2-(trimethylsilyl)phenyltrifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=95/05) afforded N-methyl-N-phenyl-4-(phenylethynyl)aniline as a brown solid (0.116 g, 82%).

(67) R.sub.f (Pet. ether/DCM=90/10): 0.57; NMR (400 MHz, CDCl.sub.3) 7.52 (d, J=7.8 Hz, 2H), 7.41 (d, J=8.7 Hz, 2H), 7.38-7.30 (m, 5H), 7.17 (d, J=7.5 Hz, 2H), 7.11 (t, J=7.3 Hz, 1H), 6.87 (d, J=8.7 Hz, 2H), 3.55 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.01, 148.33, 132.68, 131.52, 129.65, 128.41, 127.84, 124.00, 123.91, 123.76, 116.91, 113.53, 90.22, 88.11, 40.28. HRMS (ESI) calculated [M+H].sup.+ for C.sub.21H.sub.18N: 284.1434. found: 284.1470. FTIR (cm.sup.1): 3058, 3036, 2927, 2815, 2211 (CC triple bond), 1610, 1591, 1556, 1513, 1495, 1348, 1268, 1254, 1192, 1130, 1115, 1081, 1069, 1026, 869, 823, 755, 691.

Example 17

Synthesis of N-Methyl-N-phenylnaphthalen-1-amine

(68) ##STR00026##

(69) Following the general procedure, treatment of N,N-dimethyl naphthalen-1-amine (0.086 g, 83 L, 0.50 mmol) with 2-(trimethylsilyl)phenyltrifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded N-methyl-N-phenylnaphthalen-1-amine as a colourless oil (0.115 g, 98%).

(70) R.sub.f (Pet. ether/DCM=90/10): 0.56; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.93 (t, J=8.7 Hz, 2H), 7.83 (d, J=8.1 Hz, 1H), 7.55-7.51 (m, 2H), 7.46 (t, J=7.1 Hz, 1H), 7.40 (d, J=7.3 Hz, 1H), 7.20 (t, J=7.4 Hz, 2H), 6.77 (t, J=7.3 Hz, 1H), 6.66 (d, J=8.1 Hz, 2H), 3.43 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 150.22, 145.48, 135.25, 131.44, 129.05, 128.58, 126.76, 126.58, 126.47, 126.35, 125.37, 123.95, 117.32, 113.64, 40.32. HRMS (ESI) calculated [M+H].sup.+ for C.sub.17H.sub.16N: 234.1277. found: 234.1293. FTIR (cm.sup.1): 3058, 2931, 2881, 2811, 1600, 1575, 1498, 1453, 1394, 1338, 1297, 1266, 1243, 1187, 1140, 1106, 1032, 1010, 885, 867, 806, 776, 750, 693.

Example 18

Synthesis of 5-(Methyl (phenyl)amino)naphthalene-1-sulfonyl chloride

(71) ##STR00027##

(72) Following the general procedure, treatment of 5-(dimethylamino)naphthalene-1-sulfonyl chloride (0.067 g, 0.25 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.149 g, 1214, 0.50 mmol) in the presence of KF (0.058 g, 1.0 mmol), 18-crown-6 (0.264 g, 1.0 mmol) and (NH.sub.4)HCO.sub.3 (0.020 g, 0.25 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=90/10) afforded 5-(methyl(phenyl)amino)naphthalene-1-sulfonyl chloride as a yellow oil (0.050 g, 61%).

(73) R.sub.f (Pet. ether/DCM=80/20): 0.30; .sup.1H NMR (400 MHz, CDCl.sub.3) 8.49 (dd, J.sub.1=8.7 Hz, J.sub.2=2.6 Hz, 1H), 8.39-8.36 (m, 2H), 7.80 (t, J=8.1 Hz, 1H), 7.57-7.54 (m, 2H), 7.19 (t, J=8.0 Hz, 2H), 6.81 (t, J=7.3 Hz, 1H), 6.63 (d, J=7.9 Hz, 2H), 3.42 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 150.01, 147.01, 132.99, 132.47, 131.63, 131.62, 130.43, 130.10, 129.30, 126.89, 124.58, 122.59, 118.63, 114.54, 40.82. HRMS calculated [M].sup.+ for C.sub.17H.sub.14ClNO.sub.2S: 331.0434. found: 331.0812. HRMS data was recorded on Synapt MALDI-MS (Waters, UK) using Synapt MALDI-MS (Waters, UK) or AB SCIEX TofTof 5800 using -cyano-4-hydroxycinnamic acid as the solid matrix. FTIR (cm.sup.): 3329, 3061, 2928, 1600, 1572, 1498, 1415, 1400 (SO), 1341, 1261, 1223, 1211 (SO), 1148, 1110, 1044, 832, 792, 773, 748, 694, 640, 591.

Example 19

Synthesis of 4,4-(Phenylmethylene)bis(N-methyl-N-phenylaniline

(74) ##STR00028##

(75) Following the general procedure, treatment of 4,4-(phenylmethylene)bis(N,N-dimethylaniline) (0.082 g, 0.25 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=80/20) afforded 4,4-(phenylmethylene)bis(N-methyl-N-phenylaniline) as a green oil (0.088 g, 78%).

(76) R.sub.f (Pet. ether/DCM=80/20): 0.30; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.30-7.17 (m, 9H), 7.05-7.00 (m, 8H), 6.96-6.91 (m, 6H), 5.44 (s, 1H), 3.29 (s, 6H). .sup.13C NMR (100 MHz, CDCl.sub.3): 149.13, 147.25, 144.70, 137.27, 130.20, 129.49, 129.25, 128.38, 126.27, 121.12, 120.48, 120.25, 55.72, 40.35. HRMS calculated [M+H].sup.+ for C.sub.33H.sub.30N.sub.2: 455.2482. found: 455.1764. HRMS data was recorded on Synapt MALDI-MS (Waters, UK) using Synapt MALDI-MS (Waters, UK) or AB SCIEX TofTof 5800 using -Cyano-4-hydroxycinnamic acid as the solid matrix. FTIR (cm.sup.1): 3083, 3058, 3026, 2935, 2876, 2841, 1594, 1568, 1496, 1451, 1342, 1298, 1273, 1253, 1186, 1156, 1131, 1117, 1086, 1067, 1029, 1016, 868, 820, 797, 752, 711, 697.

Example 20

Synthesis of Ethyl (E)-3-(4-(methyl (phenyl)amino)phenyl)acrylate

(77) ##STR00029##

(78) Following the general procedure, treatment of ethyl (E)-3-(4-(dimethylamino)phenyl)acrylate (0.110 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=98/02) afforded Ethyl (E)-3-(4-(methyl(phenyl)amino)phenyl)acrylate as a yellow oil (0.130 g, 93%).

(79) R.sub.f (Pet. ether/EtOAc=95/05): 0.50; NMR (400 MHz, CDCl.sub.3) 7.63 (d, J=16.0 Hz, 1H), 7.40-7.35 (m, 4H), 7.19-7.14 (m, 3H), 6.82 (d, J=8.8 Hz, 2H), 6.25 (d, J=16.0 Hz, 1H), 4.25 (q, J=7.1 Hz, 2H), 3.35 (s, 3H), 1.33 (t, J=7.1 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 167.83, 150.77, 147.88, 144.80, 129.77, 129.48, 125.03, 125.84, 124.68, 115.79, 113.98, 60.30, 40.28, 14.50. HRMS (ESI) calculated [M+H].sup.+ for C.sub.18H.sub.20O.sub.2N: 282.1489. found: 282.1484. FTIR (cm.sup.1): 3061, 3035, 2980, 2936, 2902, 1705 (ester), 1628, 1606, 1591, 1559, 1515, 1495, 1350, 1330, 1258, 1215, 1166, 1137, 1122, 1040, 983, 868, 821, 768, 700.

Example 21

Synthesis of (E)-N-Methyl-4-(4-nitrostyryl)-N-phenylaniline

(80) ##STR00030##

(81) Following the general procedure, treatment of (E)-N,N-dimethyl-4-(4-nitrostyryl)aniline (0.067 g, 0.25 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.090 g, 73 L, 0.3 mmol) in the presence of KF (0.035 g, 0.6 mmol), 18-crown-6 (0.159 g, 0.6 mmol) and (NH.sub.4)HCO.sub.3 (0.020 g, 0.25 mmol) in THF (1.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=92/8) afforded (E)-N-Methyl-4-(4-nitrostyryl)-N-phenylaniline as a colourless oil (0.064 g, 78%).

(82) R.sub.f (Pet. ether/EtOAc=90/10): 0.56; .sup.1H NMR (400 MHz, CDCl.sub.3) 8.10 (d, J=8.7 Hz, 2H), 7.49 (d, J=8.8 Hz, 2H), 7.34 (d, 0.1=8.6 Hz, 2H), 7.28, (t, J=7.6 Hz, 2H) 7.17 (d, J=10.7 Hz, 1H), 7.11-7.08 (m, 2H), 7.04 (t, J=7.4 Hz, 1H), 6.88 (d, J=16.2 Hz, 1H), 6.83 (d, J=8.9 Hz, 2H), 3.28 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.70, 148.28, 146.29, 144.78, 133.38, 129.68, 128.23, 127.42, 126.43, 124.29, 123.97, 123.89, 123.09, 117.21, 40.35. HRMS calculated [M+H].sup.+ for C.sub.21H.sub.19O.sub.2N.sub.2: 331.1441. found: 331.1438. FTIR (cm.sup.1): 2927, 1606, 1585, 1509 (NO.sub.2), 1339 (NO.sub.2), 1254, 1188, 1114, 971, 837, 806, 776, 749.

Example 22

Synthesis of 5-(4-(Methyl (phenyl)amino)phenyl)thiophene-2-carbaldehyde

(83) ##STR00031##

(84) Following the general procedure, treatment of 5-(4-(dimethylamino)phenyl)thiophene-2-carbaldehyde (0.116 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=90/10) afforded 5-(4-(methyl(phenyl)amino)phenyl)thiophene-2-carbaldehyde as a green colour solid (0.079 g, 54%).

(85) R.sub.f (Pet. ether/EtOAc=90/10): 0.39; .sup.1H NMR (400 MHz, CDCl.sub.3) 9.86 (s, 1H), 7.71 (d, J=3.9 Hz, 1H), 7.56 (d, J=8.7 Hz, 2H), 7.40, (t, J=7.7 Hz, 2H) 7.29 (d, J=3.5 Hz, 1H), 7.22-7.16 (m, 3H), 6.91 (d, J=8.8 Hz, 2H), 3.39 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 182.66, 155.46, 150.21, 148.01, 140.86, 138.03, 129.79, 127.44, 124.64, 124.46, 123.65, 122.31, 116.58, 40.32. HRMS calculated [M+H].sup.+ for C.sub.18H.sub.16ONS: 294.0947. found: 294.0941. FTIR (cm.sup.1): 3373, 2925, 2855, 2726, 1655 (CHO), 1590, 1458, 1377, 1231, 1081, 801, 773.

Example 23

Synthesis of N,3,4-trimethyl-N-phenylaniline

(86) ##STR00032##

(87) Following the general procedure, treatment of N,N-dimethylaniline (0.061 g, 65 L, 0.50 mmol) with 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.196 g, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50, mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=96/4) afforded N,3,4-trimethyl-N-phenylaniline as a colourless oil (0.098 g, 93%).

(88) R.sub.f (Pet. ether/DCM=90/10): 0.50; .sup.1H NMR (400 MHz, CDCl.sub.3) 87.30-7.26 (m, 2H), 7.13 (d, J=8.01 Hz, 1H), 6.98-6.89 (m, 5H), 3.34 (s, 3H), 2.29 (s, 3H), 2.28 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.51, 147.0, 137.68, 131.15, 130.55, 129.11, 124.31, 120.43, 119.64, 118.0, 40.49, 20.10, 19.21. HRMS calculated [M+H].sup.+ for C.sub.15H.sub.18N: 212.1434. found: 212.1433. FTIR (cm.sup.1): 3022, 2920, 2809, 1595, 1496, 1450, 1343, 1300, 1117, 998, 751.

Example 24

Synthesis of N-methyl-N-phenylbenzo[d][1,3]dioxol-5-amine

(89) ##STR00033##

(90) Following the general procedure, treatment of N,N-dimethylaniline (0.061 g, 65 L, 0.50 mmol) with 6-(trimethylsilyl)benzo[d][1,3]dioxol-5-yl trifluoromethanesulfonate (0.205 g, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50, mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=96/4) afforded N-methyl-N-phenylbenzo[d][1,3]dioxol-5-amine (0.106 g, 94%).

(91) R.sub.f (Pet. ether/DCM=90/10): 0.33; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.29-7.23 (m, 2H), 6.88-6.81 (m, 4H), 6.70-6.63 (m, 2H), 5.99 (s, 2H), 3.28 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.70, 148.39, 144.12, 143.80, 129.10, 119.11, 117.41, 116.69, 108.71, 106.31, 101.33, 40.78. HRMS calculated [M+H].sup.+ for C.sub.14H.sub.14O.sub.2N: 228.1019. found: 228.1013. FTIR (cm.sup.1): 2886, 2810, 1598, 1577, 1485, 1326, 1241, 1214, 1115, 1038, 939, 927, 751.

Example 25

Synthesis of 3,4-Difluoro-N-methyl-N-Phenylaniline

(92) ##STR00034##

(93) Following the general procedure, treatment of N,N-dimethylaniline (0.061 g, 65 L, 0.50 mmol) with 4,5-difluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.201 g, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50, mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=96/4) afforded 3,4-difluoro-N-methyl-N-phenylaniline 3w as a colorless oil (0.097 g, 88%).

(94) R.sub.f (Pet. ether/DCM=90/10): 0.65; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.89 (t, J=9.7 Hz, 2H), 7.57-7.52 (m, 4H), 7.25-7.18 (m, 1H), 7.09-7.04 (m, 1H), 2.85 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 170.75 (dd, J.sub.1=16.8 Hz, J.sub.2=307.5 Hz), 166.46, 163.69 (dd, J.sub.1=16.5 Hz, J.sub.2=302.0 Hz), 163.36 (dd, J.sub.1=2.8 Hz, J.sub.2=9.7 Hz), 142.67, 134.01, 132.17, 127.42 (d, J=21.4 Hz), 124.4 (q, J=3.07), 116.3 (d, J=24.2 Hz), 31.54. HRMS calculated [M+H].sup.+ for C.sub.13H.sub.12NF.sub.2: 220.0932. found: 220.0930. FTIR (cm.sup.1): 3038, 2887, 2815, 1597, 1516, 1495, 1277 (CF), 1119, 1083, 828, 774.

Example 26

Synthesis of N,2,5-trimethyl-N-Phenylaniline

(95) ##STR00035##

(96) Following the general procedure, treatment of N,N-dimethylaniline (0.061 g, 65 L, 0.50 mmol) with 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.196 g, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50, mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=96/4) afforded N,2,5-trimethyl-N-phenylaniline as a colorless oil (0.067 g, 64%).

(97) R.sub.f (Pet. ether/DCM=90/10): 0.65; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.22-7.18 (m, 3H), 7.03 (d, J=7.69 Hz, 1H), 6.99 (s, 1H), 6.73 (t, J=7.22 Hz, 1H), 6.73 (d, J=7.91 Hz, 2H), 3.23 (s, 3H) 2.33 (s, 3H), 2.12 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.31, 146.7, 137.32, 133.60, 131.24, 129.07, 128.93, 127.32, 127.32, 116.74, 112.88, 39.13, 20.99, 17.52. HRMS calculated [M+H].sup.+ for C.sub.15H.sub.18N: 212.1434. found: 212.1432. FTIR (cm.sup.): 3088, 3024, 2921, 2809, 1575, 1499, 1450, 1340, 1115, 1066, 815, 748.

Example 27

Synthesis of 3-Methoxy-N-methyl-N-Phenylaniline

(98) ##STR00036##

(99) Following the general procedure, treatment of N,N-dimethylaniline (0.061 g, 65 L, 0.50 mmol) with 2-methoxy-6-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.197 g, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=96/4) afforded 3-Methoxy-N-methyl-N-phenylaniline as a colorless oil (0.087 g, 95%).

(100) R.sub.f (Pet. ether/DCM=90/10): 0.33; NMR (400 MHz, CDCl.sub.3) 7.32 (t, J=8.1 Hz, 2H), 7.19 (d, J=7.9 Hz, 1H), 7.10 (d, J=7.9 Hz, 2H), 7.02, (t, J=7.5 Hz, 1H), 6.62 (d, J=8.3 Hz, 1H), 6.58 (s, 1H) 6.52 (d, J=7.9 Hz, 1H), 3.79 (s, 3H), 3.34 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 160.67, 150.50, 148.98, 129.88, 129.36, 122.11, 121.72, 112.33, 106.04, 105.72, 55.30, 40.42. HRMS calculated [M+H].sup.+ for C.sub.14H.sub.16ON: 214.1226. found: 214.1229. FTIR (cm.sup.1): 2999, 2936, 2834, 1595, 1494, 1437, 1436, 1347, 1169, 1127, 1049, 991, 754.

Example 28

Synthesis of N-Methyl-N-Phenylnaphthalen-2-amine

(101) ##STR00037##

(102) Following the general procedure, treatment of N,N-dimethylaniline (0.061 g, 65 L, 0.50 mmol) with 2-(trimethylsilyl)naphthalen-1-yl trifluoromethanesulfonate (0.209 g, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50, mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=96/4) afforded N-methyl-N-phenylnaphthalen-2-amine as a colorless oil (0.112 g, 96%).

(103) R.sub.f (Pet. ether/DCM=90/10): 0.48; NMR (400 MHz, CDCl.sub.3) 7.79 (d, J=8.18 Hz, 1H), 7.74 (t, J=7.7 Hz, 2H), 7.48-7.45 (m, 1H), 7.39-7.34 (m, 4H), 7.29-7.25 (m, 1H), 7.16 (d, J=7.74, 2H), 7.07 (t, J=7.25, 1H), 3.47 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.16, 146.68, 134.80, 129.42, 129.26, 128.71, 127.67, 126.87, 126.40, 123.87, 122.13. 121.92, 121.53, 114.74, 40.78. HRMS calculated [M+H].sup.+ for C.sub.17H.sub.16N: 234.1277. found: 234.1274. FTIR (cm.sup.1): 3056, 2940, 2811, 1628, 1593, 1494, 1364, 1297, 1281, 1321, 1119, 813, 747, 699.

Example 29

Synthesis of N,4-dimethyl-N-phenylaniline and N,3-dimethyl-N-phenylaniline

(104) ##STR00038##

(105) Following the general procedure, treatment of N,N-dimethylaniline (0.061 g, 65 L, 0.50 mmol) with 4-methyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.187 g, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50, mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet ether/DCM=96/4) afforded N,4-dimethyl-N-phenylaniline and N,3-dimethyl-N-phenylaniline as a mixture of regioisomers in 1.3:1 ratio as a colorless oil (0.092 g, 93%).

(106) R.sub.f (Pet ether/DCM=90/10): 0.55; .sup.1H NMR (400 MHz, CDCl.sub.3) of Major isomer; 7.35-7.31 (m, 2H), 7.24 (t, J=7.6 Hz, 1H), 7.09-7.08 (m, 2H), 6.96-6.91 (m, 3H), 6.87 (d, J=7.2 Hz, 1H), 3.37 (s, 3H), 2.37 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) of Major isomer; 149.23, 149.12, 139.14, 129.15, 122.69, 121.57, 120.22, 118.28, 40.40, 21.70. .sup.1H NMR (400 MHz, CDCl.sub.3) of Minor isomer; 7.30-7.28 (m, 2H), 7.18 (d, J=8.20 Hz, 2H), 7.07-7.06 (m, 2H), 7.03-6.99 (m, 3H), 3.35 (s, 3H), 2.39 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) of Minor isomer; 149.45, 146.68, 132.19, 130.04, 129.26, 122.49, 121.06, 119.91, 118.04, 40.46, 20.88. HRMS calculated [M+H].sup.+ for C.sub.14H.sub.16N: 198.1277. found: 198.1275. FTIR (cm.sup.1): 3026, 2920, 2874, 2810, 1595, 1509, 1342, 1260, 1129, 1090, 1028, 992.

Example 30

Synthesis of N-Methyl-N-(p-tolyl)benzo[d][1,3]dioxol-5-amine

(107) ##STR00039##

(108) To a flame-dried round bottom flask equipped with a magnetic stir bar were added N,N dimethyl-N-(p-tolyl)benzo[d][1,3]dioxol-4-aminium salt (6.HOTf) (0.102 g, 0.25 mmol), 18-crown-6 (0.158 g, 0.60 mmol), KF (0.035 g, 0.60 mmol) and (NH.sub.4)HCO.sub.3 (0.020 g, 0.25 mmol) at room temperature (27 C.). Then the mixture was dissolved in THF (1.0 mL) under argon atmosphere and round bottom flask kept in a pre-heated oil bath at 60 C. for 12 h. The reaction mixture cooled and the residue on column chromatography (Pet. ether/DCM=90/10) afforded N-methyl-N-(p-tolyl)benzo[d][1,3]dioxol-5-amine as a colorless oil (0.043 g, 70%).

(109) R.sub.f (Pet. ether/DCM=80/20): 0.32; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.07 (d, J=8.3 Hz, 2H), 6.83 (d, J=8.3 Hz, 2H), 6.76 (d, J=8.3 Hz, 1H), 6.62 (d, J=2.1 Hz, 1H), 6.53 (dd, J.sub.1=8.3 Hz, J.sub.2=2.1 Hz, 1H), 5.94 (s, 2H), 3.23 (s, 3H), 2.30 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 148.30, 147.52, 144.58, 143.17, 129.76, 129.58, 118.67, 115.21, 108.56, 104.65, 101.17, 40.99, 20.63. HRMS (ESI) calculated [M+H].sup.+ for C.sub.15H.sub.16O.sub.2N: 242.1176. found: 242.1162. FTIR (cm.sup.1): 2920, 2883, 2808, 1611, 1514, 1504, 1485, 1324, 1284, 1241, 1214, 1155, 1113, 1039, 940, 927, 841, 811, 781, 726.

Example 31

Synthesis of N,2,5-Trimethyl-N-phenylaniline-6-d

(110) ##STR00040##

(111) Following the general procedure, treatment of N,N-dimethylaniline (0.030 g, 32 L, 0.25 mmol) with 3,6-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.098 g, 0.30 mmol) in the presence of KF (0.035 g, 0.60 mmol), 18-crown-6 (0.158 g, 0.60 mmol) and D.sub.2O (0.005 g, 4.6 L, 0.25 mmol) in THF (1.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/EtOAc=99/01) afforded N,2,5-trimethyl-N-phenylaniline-6-d as a colorless oil (0.036 g, 69%).

(112) R.sub.f (Pet. ether/DCM=90/10): 0.65; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.22-7.18 (m, 3H), 7.04 (d, J=7.7 Hz, 1H), 7.00 (s, 32% H), 6.73 (t, J=7.9 Hz, 1H), 6.57 (d, J=7.9 Hz, 2H), 3.24 (s, 3H) 2.33 (s, 3H), 2.13 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 149.34, 146.73, 146.67, 137.32, 137.23, 133.60, 133.58, 131.24, 129.07, 128.92, 127.32, 116.77, 112.92, 39.15, 20.91, 17.51. HRMS(ESI) calculated [M+H].sup.+ for C.sub.15H.sub.17.sup.2HN: 213.1497. found: 213.1490.

Example 32

Synthesis of 3-(Methyl(phenyl)amino)phenol, 3-Methoxy-N-methyl-N-phenylaniline and N-Methyl-3-phenoxy-N-phenylaniline

(113) Following the general procedure, treatment of 3-(dimethylamino)phenol (0.069 g, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) and (NH.sub.4)HCO.sub.3 (0.040 g, 0.50 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography afforded three product as follows, 3-(methyl(phenyl)amino)phenol as a brown oil (0.030 g, 30%), 3-methoxy-N-methyl-N-phenylaniline as a colorless oil (0.057 g, 53%), and N-methyl-3-phenoxy-N-phenylaniline as a colorless oil (0.020 g, 14%).

(114) ##STR00041##

3-(Methyl(phenyl)amino)phenol

(115) R.sub.f (Pet. ether/EtOAc=90/10): 0.30; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.31 (t, J=7.9 Hz, 2H), 7.12-7.08 (m, 3H), 7.03 (t, J=7.4 Hz, 1H), 6.53 (dd, J.sub.1=8.1 Hz, J.sub.2=1.5 Hz, 1H), 6.44 (t, J=2.2 Hz, 1H), 6.39 (dd, J.sub.1=8.1 Hz, J.sub.2=2.3 Hz, 1H), 3.29 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 156.57, 150.71, 148.88, 130.11, 129.42, 122.59, 122.49, 111.43, 107.49, 105.90, 40.38. HRMS (ESI) calculated [M+H].sup.+ for C.sub.13H.sub.14ON: 200.1070. found: 200.1072. FTIR (cm.sup.1): 3381, 3060, 3037, 2929, 2814, 1591, 1496, 1459, 1349, 1275, 1195, 1165, 1126, 1092, 1027, 992, 955, 943, 829, 758, 693.

3-Methoxy-N-methyl-N-phenylaniline

(116) 3-(dimethylamino)phenol on reaction with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate resulted in the formation of 3-(methyl(phenyl)amino)phenol, in situ, the free phenolic group is methylated or arylated to furnish the 3-methoxy-N-methyl-N-phenylaniline (Example No. 27) and N-methyl-3-phenoxy-N-phenylaniline (Example No. 28) respectively.

(117) ##STR00042##

(118) R.sub.f (Pet. ether/DCM=90/10): 0.47; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.31 (t, J=7.9 Hz, 2H), 7.19 (t, J=8.2 Hz, 1H), 7.10 (d, J=7.9 Hz, 2H), 7.02 (t, J=7.4 Hz, 1H), 6.61 (dd, J.sub.1=8.1 Hz, J.sub.2=1.8 Hz, 1H), 6.57 (t, J=2.2 Hz, 1H), 6.52 (dd, J.sub.1=8.1, J.sub.2=2.3 Hz, 1H), 3.78 (s, 3H), 3.33 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 160.66, 150.50, 148.98, 129.89, 129.36, 122.11, 121.73, 112.33, 106.04, 105.71, 55.30, 40.42. HRMS (ESI) calculated [M+H].sup.+ for C.sub.14H.sub.16ON: 214.1226. found: 214.1226. FTIR (cm.sup.1): 2999, 2932, 2834, 1592, 1493, 1467, 1347, 1274, 1215, 1169, 1127, 1094, 1048, 929, 754.

N-Methyl-3-phenoxy-N-phenylaniline

(119) ##STR00043##

(120) R.sub.f (Pet. ether/DCM=90/10): 0.50; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.34-7.30 (m, 4H), 7.17 (t, J=8.1 Hz, 1H), 7.12 (d, J=7.8 Hz, 2H), 7.08 (t, J=7.4 Hz, 1H), 7.05-7.02 (m, 3H), 6.69 (dd, J.sub.1=8.2 Hz, J.sub.2=1.5 Hz, 1H), 6.67 (t, J=2.0 Hz, 1H), 6.51 (dd, J.sub.1=8.2, J.sub.2=1.5 Hz, 1H), 3.30 (s, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 158.12, 157.44, 150.75, 148.70, 130.03, 12937, 129.49, 123.15, 122.87, 122.68, 118.84, 113.63, 110.50, 109.33, 40.41. HRMS (ESI) calculated [M+H].sup.+ for C.sub.19H.sub.18ON: 276.1383. found: 276.1385. FTIR (cm.sup.1): 3063, 3038, 2925, 2814, 1588, 1488, 1347, 1260, 1222, 1163, 1125, 1092, 1072, 1024, 993, 959, 847, 769, 754, 691.

Example 33

Synthesis of N-Ethyl-N-phenylaniline

(121) ##STR00044##

(122) Following the general procedure, treatment of N,N-diethylaniline (0.075 g, 81 L, 0.50 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol), 18-crown-6 (0.317 g, 1.20 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded N-Ethyl-N-phenylaniline as a colorless oil (0.060 g, 61%).

(123) R.sub.f (Pet. ether/DCM=90/10): 0.66; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.28-7.25 (m, 4H), 7.00 (d, J=7.5 Hz, 4H), 6.94 (t, J=7.4 Hz, 2H), 3.80-3.76 (m, 2H), 1.24-1.21 (m, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) 147.89, 129.38, 121.22, 121.06, 46.54, 12.82. HRMS (ESI) calculated [M+H].sup.+ for C.sub.14H.sub.16N: 198.1277. found: 198.1277. FTIR (cm.sup.1): 3060, 3036, 2972, 2929, 2870, 1588, 1495, 1371, 1348, 1261, 1241, 1131, 1100, 783, 748, 693.

Example 34

Synthesis of N-Phenyl-N-(2-vinylbenzyl)aniline

(124) ##STR00045##

(125) Treatment of 1,2,3,4-tetrahydroisoquinoline (0.033 g, 32 L, 0.25 mmol) with 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.179 g, 146 L, 0.60 mmol) in the presence of KF (0.070 g, 1.20 mmol) and 18-crown-6 (0.317 g, 1.20 mmol) in THF (2.0 mL) at 60 C. for 12 h followed by column chromatography (Pet. ether/DCM=98/02) afforded N-phenyl-N-(2-vinylbenzyl)aniline as a white solid (0.060 g, 86%).

(126) R.sub.f (Pet. ether/DCM=90/10): 0.65; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.50 (d, J=7.0 Hz, 1H), 7.42 (d, J=7.0 Hz, 1H), 7.27-7.18 (m, 6H), 7.07 (d, J=7.9 Hz, 4H), 7.02-6.94 (m, 3H), 5.68 (d, J=17.3 Hz, 1H), 5.37 (d, J=11.0 Hz, 1H), 5.04 (s, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) 148.06, 136.10, 135.49, 133.76, 129.40, 128.07, 127.08, 126.85, 126.23, 121.59, 120.77, 116.66, 54.37. HRMS (ESI) calculated [M+H].sup.+ for C.sub.21H.sub.20N: 286.1595. found: 286.1592. FTIR (cm.sup.1): 3061, 3028, 2921, 2853, 1579, 1485, 1338, 1227, 1062, 986, 914, 848.

ADVANTAGES OF THE INVENTION

(127) 1. Transition-Metal free approach. 2. High yields. 3. Use of Simple and easily available starting materials. 4. Synthesis of Arylamines which play a key role in a number of fields like Pharmaceuticals, Agrochemicals, Dyes, Electronic materials.