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—*W^U Formate with a Drop of Trifluoroacetic Acid Was Re- XXX Fluxed for 0.5 to 3 H A Simple Route to /V-Methylarylamines Z. DASZKIEWICZ, A. DOMAŇSKI, and J. B. KYZIOt Instytut Chemii, Wyžsza Szkoia Pedagogiczna, PL-45 052 Opole Received 9 April 1992 Thirteen ring-substituted anilines were transformed into corresponding formanilides by the action of n-butyl formate in the presence of trifluoroacetic acid and then reduced with lithium aluminium hydride to /V-methylanilines in total yields 40—70 %. The method can be employed for methylation of primary and secondary amino groups bound to aromatic and heteroaromatic systems provided that they are neither sterically hindered nor strongly conjugated with other substituents. The general method of /V-alkylamines preparation, EXPERIMENTAL i.e. alkylation with alkyl halides or inorganic acids esters and reductive alkylations with carbonyl com­ The starting, amines were commercial reagents, pounds are of limited value as regards synthesis of pure, used without purification. The progress of re­ /V-methylaniline and its derivatives. Reaction of ani­ actions was followed by the TLC method (Silufol; line with methyl iodide affords the quaternary am­ Kavalier, Votice) using PhMe—AcOEt (<pr = 2 : 1) and monium salt [1], with less reactive methyl sulfate CHCI3—MeOH («ft = 24 : 1 to 5 : 1) mixtures as the a mixture of compounds is obtained from which developing systems; the plates were sprayed with /V-methylaniline can be isolated as the /V-nitroso de­ 1 % rhodamine В and observed under the UV lamp. rivative [2]. Methylation of /V-tosylaniline presents no All the compounds gave satisfactory elemental such problems but the cleavage of the sulfonamide analyses. The purity of /V-methylarylamines was bond requires very severe conditions [3], hence only controlled on the gas Chromatograph 900 some aniline derivatives can be /V-methylated in this (Perkin—Elmer) equipped with the flame ionization way. detector and the 2.4 m x 2 mm column packed with Reductive methylation of anilines having substi­ the silicone oil OV-17 (3 %) on Chromosorb G-AW- tuted the most reactive sites in the benzene ring DMCS (0.149—0.177 mm). The analyses were per­ gives /V,/V-dimethyl derivatives but other substrates, formed under isothermal conditions at 200 °C; pu­ when methylated according to the Eschweiler—Clark rity of a product was 98—99 % unless stated other­ procedure yield mainly resins [4, 5]. Polyconden- wise. sation can be excluded if sodium borohydride is used Electron impact (70 eV) mass spectra were regis­ as the reducing agent but again /V-methylaniline tered on the MX 1321 spectrometer (Scientific In­ cannot be obtained in such a way [6]. struments, USSR). 1H and 13C NMR spectra were In this report we describe a simple method of recorded on the spectrometer BS 567A (Tesla) (2.3 /V-methylarylamines preparation involving formylation T) in CDCI3 with TMS as the standard. The infrared of the arylamine with subsequent reduction of the spectra were recorded on the Specord IR 75 instru­ corresponding formanilide (Scheme 1). ment (Zeiss, Jena) in the KBr pellets or as a liquid film. NH2 NHCHO NHCH3 Substituted Formanilides lla-llm HCOOBu r<^N LiAIH4 r^Tl The mixture of a ring-substituted aniline / (0.10 Ô mol) and the appropriate amount (Table 1) of n-butyl —*w^u formate with a drop of trifluoroacetic acid was re- XXX fluxed for 0.5 to 3 h. The solution was left overnight la-lm lla-llm llla-lllm in an ice-box, the precipitate was collected by filtra­ tion and purified by crystallization from a proper l-HI a b c d e f g solvent. If the precipitate was not formed, the solu­ X 2-Me 4-Me 2,6-Me benzo[2,3] 4-NMe 2-OMe 3-OMe 2 2 tion was heated to the boiling point, diluted with the h i j k im equal volume of n-hexane and cooled again below X 4-OMe 3-CI 4-CI 4-Br 3-N0 4-N0 2 2 0 °C. The crude product was collected and recrys- Scheme 1 tallized giving a pure formanilide //. The yields and Chem. Papers 47 (2) 109-113 (1993) 109 Z. DASZKIEWICZ, A. DOMANSKI, J. B. KYZIOt melting points of pure products are collected in /V-Methylaniline /// (1 cm3, ca. 5 mmol) was dis­ Table 1. solved in 8 cm3 of the 1 M solution of tosyl chloride in methylene chloride. 2 M aqueous potassium hy­ droxide (8 cm3) was added and the mixture shaken Substituted A/-Methylanilines lila—Ulm and for 15 min. The precipitate was collected by filtra­ Their Tosylates tion and crystallized from n-hexane or methanol. The melting points of the ring-substituted /V-methyl-Л/- A ring-substituted formanilide // (0.10 mol) was tosylanilines are given in Table 3. dissolved in absolute tetrahydrofuran (50 cm3) and the solution was slowly dropped into intensely stirred suspension of lithium aluminium hydride (3.80 g; 0.10 RESULTS mol) in tetrahydrofuran (50 cm3). The mixture was stirred at room temperature for ca. 1 h and decom­ Formylation of the primary, ring-substituted anilines posed. Acetone (50 cm3) was cautiously dropped in / was carried out using n-butyl formate as the acyla- and then 50 % aqueous potassium hydroxide was ting agent. It should be mentioned that carefully added in small portions until the aluminates were purified ester, free of formic acid is inactive and the precipitated. The mixture was filtered, the precipi­ reaction must be catalyzed with trifluoroacetic acid. tate washed with tetrahydrofuran and discarded. The Minimum amounts of the formate were used suffi­ combined filtrates were evaporated and the residue ciently to obtain homogeneous reaction mixtures. distilled in vacuum. Solid residues (lllf, lllh, Uli, Ulm) Most of the formanilides (cf. Tables 1 and 2) crys­ were purified by crystallization. The results are col­ tallized from cold reaction mixtures, in some cases lected in Table 3. (e.g. lib, llf, llg) the solutions were diluted with the Table 1. Characterization of Formanilides Reaction Yield M.p./°C Compound n(R)/n(S)a M.p./°C Ref. time/h % (Solvent) //a 1.3 1 80 56-59 (PhMe) 56.5-57.5 [7] lib 1.3 0.5 70 53-54 (MeOH) 52 [7] lie 2.5 0.1 47 166-167 (ЕЮН) 164-165 [8] lid 9.0 2 88 140-141 (PhMe) 138.5 [7] lie 7.0 0.1 82 147-148 (PhMe) - llf 2.8 1 84 83-84 (PhMe) 83.5 [9] iig 1.3 0.5 89 58-60 (MeOH) 57 [10] llh 3.0 0.5 69 78—79 (Octane) 80-81 [11] III 3.8 1 86 56-58 (PhH) 57-58 [12] HI 3.7 3 63 103-105 (PhH) 102 [13] Ilk 4.9 2 87 116-117 (PhMe) 119 [13] lie 3.5 3 83 134-135 (AcEt) 134 [14] llm 4.0 2 77 199-200 (AcEt) 194-195 [15] a) The amount of substance ratio of n-butyl formate to the aniline. Table 2. Spectral Characteristics of Formanilides IR, v/cm"1 Compound Mass spectra, m/z (IJ%) Amide bands IIa 1550, 1665, 3240 135 (M+, 28), 118 (6), 107 (22), 106 (59), 79 (11), 77 (18), 29 (100) IIb 1520, 1690, 3190 135 (M+, 98), 107 (36), 106 (100), 79 (14), 77 (23), 51 (11), 29 (6) lie 1525, 1655, 3230 149 (M+, 62), 132 (26), 120 (100), 106 (60), 91 (35), 29 (3) lid 1540, 1655, 3220 171 (M+, 68), 143 (88), 116 (33), 115 (100), 89 (17), 29 (47) lie 1530, 1630 164 (M\ 3), 136 (100), 121 (15), 120 (6), 93 (4), 29 (5) llf 1530, 1655, 3250 151 (M+, 32) , 123 (15), 108 (66), 80 (100), 65 (20), 29 (20) ng 1520, 1680, 3200 151 (M+, 100), 123 (80), 108 (4), 94 (77), 80 (62), 29 (19) llh 1510, 1655, 3240 151 (M+, 6), 122 (4), 108 (18), 80 (16), 29 (100) Hi 1595, 1695, 3200 157 (25), 155 (M+, 81), 129 (31), 127 (100), 92 (32), 29 (100) Hi 1540, 1620, 3250 157 (25), 155 (M+, 75), 129 (28), 127 (100), 92 (32), 29 (7) Ilk 1530, 1670, 3280 201 (99), 199 (M+, 100), 173 (69), 171 (73), 92 (82), 65 (61) lit 1545, 1680, 3260 166 (M+, 100), 138 (25), 120 (6), 92 (76), 65 (74), 29 (27) llm 1550, 1680, 3255 166 (M+, 100), 138 (9), 136 (3), 108 (24), 92 (32), 64 (74) 110 Chem. Papers 47 (2) 109-113 (1993) A/-METHYLARYLAMINES Table 3. Characterization of /V-Methylanilines and Their Tosylates Yield B.p./°C (p/hPa) /V-Tosyl derivatives Compound % M.p./°C (Solvent) M.p./°C (Solvent) M.p./°C Ref. Ilia 90 70(7) 73-74 (Hexane) 86 [16] lllb 69 75(11) 62—63 (Hexane) 60 [16] lllc 70 65 (5) 122-123 (MeOH) - Hid 83 97 (0.7) 127-128 (Hexane) 124-125 [17] Hie 72 102 (3) 91-92 (Hexane) - lllf 45 80 (5) 104-105 (Hexane) 100 [6] 33-34 (Hexane)a nig 88 108 (9) 58-59 (MeOH) - lllh 84 109 (11) 72-73 (MeOH) 68-69 [16] 35-36 (Hexane)b Uli 91 99 (5) 80—81 (Hexane) - mi 65 74 (0.7) 96-97 (MeOH) 96 [16] Ulk 63 96 (0.5)c 88—89 (Hexane) - HU 68 63-64 (aq. EtOH)d 112-113 (Hexane) 139 [18] Ulm 42 151-152 (EtOH)e 178-179 (AcEt) 188-189 [16] Ref. give m.p.'s: a) 33-33.5 °C [9]; b) 37 °C [11]; c) 11 °C [19]; d) 65-66 °C [20]; e) 150-151 °C [21]. Table 4. 13C NMR Spectral Data (<5) of /V-Methylanilines Compound С-1 С-2 С-3 С-4 С-5 С-6 N-СНз СН3 Ilia 14 7.2 121.8 129.9 116.8 127.2 109.1 30.7 17.3 lllb 147.2 112.6 129.7 126.3 129.7 112.6 31.0 20.4 lllc 147.4 128.2 128.8 121.8 128.8 128.2 35.3 18.4 Hid 144.5 115.3 134.2 117.2 119.8 103.6 30.8 а Hie 143.9 115.9 113.8 141.9 113.8 115.9 31.6 42.0* lllf 139.3 146.9 109.2 116.4 121.3 109.4 30.4 55.4 lllg 147.5 98.2 160.8 102.2 129.9 105.6 31.6 55.0 lllh 143.6 114.9 113.7 152.1 113.7 114.9 31.6 55.8 Hli 150.4 111.8 134.9 116.9 130.1 110.8 30.5 - mi 147.9 113.4 128.9 121.5 128.9 113.4 30.6 - Ulk 148.2 113.9 131.8 108.7 131.8 113.9 30.7 - 149.9 106.0 149.6 111.9 129.7 118.7 30.6 - пиc lllm 155.2 110.4 126.2 135.5 126.2 110.4 29.1 - а) Carbons of the unsubstituted ring give signals at ô - 124.5, 125.6, 126.6, and 128.6.
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