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Synlett 2008(16): 2437-2442  
DOI: 10.1055/s-2008-1078171
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis and Reactivity of Novel α,α,β- and α,α,δ-Trichlorinated Imines

Matthias D’hooghe, Bruno De Meulenaer, Norbert De Kimpe*
Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent, Belgium
e-Mail: norbert.dekimpe@UGent.be;
Further Information

Publication History

Received 21 May 2008
Publication Date:
10 September 2008 (online)

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Abstract

A variety of different N-(2,2,3-trichloropropyli­dene)amines, N-(2,2,3-trichlorobutylidene)amines, and N-(2,2,5-trichloropentylidene)amines were synthesized for the first time, and their reactivity with regard to hydride reagents was investigated. In this way, N-(2,2,5-trichloropentylidene)amines were evaluated as substrates for the synthesis of piperidines, and N-(2,2,3-trichloropropylidene)amines and N-(2,2,3-trichlorobutylidene)amines were reduced efficiently into the corresponding novel β,β,γ-trichloro-amines by means of sodium cyanoborohydride in methanol in the presence of acetic acid. Furthermore, N-(2,2,3-trichloropropyli­dene)amines were transformed into 2-(chloromethyl)aziridines by lithium aluminium hydride in Et2O, and N-(2,2,5-trichloropentylidene)acetamide was used for the first time as a suitable substrate for the addition of oxygen, nitrogen, and sulfur nucleophiles in good yields.

Key words

trichlorinated imines - hydride reagents - trichloro­amines - 2-(chloromethyl)aziridines

    References and Notes

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14

N -(2,2,5-Trichloropentylidene)isopropylamine (3a)Bp 41-42 ˚C (0.10 Torr). ¹H NMR (270 MHz, CDCl3): δ = 1.19 (6 H, d, J = 6.3 Hz), 2.18-2.22 (2 H, m), 2.57-2.62 (2 H, m), 3.49 (1 H, septd, J = 6.3, 0.7 Hz), 3.64 (2 H, t, J = 5.9 Hz), 7.75 (1 H, d, J = 0.7 Hz). ¹³C NMR (68 MHz, CDCl3): δ = 23.5, 28.4, 40.9, 44.2, 59.8, 88.5, 157.1. IR (NaCl): ν = 1667 (C=N) cm-¹. MS (70 eV): m/z (%) = 229/231/233/235 (0.3) [M+], 194/196/198(16), 70(100); for chlorine isotopes, the reported relative intensity (%) represents the largest peak.

20

N -(2,2,5-Trichloro-1-phenoxypentyl)acetamide (9a)
Mp 130 ˚C. ¹H NMR (270 MHz, CDCl3): δ = 2.07 (3 H, s), 2.10-2.60 (4 H, m), 3.59 (2 H, t, J = 6.3 Hz), 6.18 (1 H, d, J = 10.1 Hz), 6.47 (1 H, d, J = 10.1 Hz), 7.01-7.06 (3 H, m), 7.26-7.34 (2 H, m). ¹³C NMR (68 MHz, CDCl3): δ = 23.3, 27.9, 41.4, 44.0, 81.3, 93.7, 115.9, 122.8, 129.9, 155.5, 170.2. IR (NaCl): ν = 3270 (NH), 1660 (C=O) cm-¹. MS (70 eV): m/z (%), no [M+] = 149 (19), 112 (18), 110 (20), 77 (100), 49 (22); for chlorine isotopes, the reported relative intensity (%) represents the largest peak. Anal. Calcd for C13H16Cl3NO2: C, 48.10; H, 4.97; N, 4.31. Found: C, 48.33; H, 5.20; N, 4.15.

23

N -(2,2,3-Trichloropropylidene)isopropylamine (14a)
Bp 24-26 ˚C (0.01 Torr). ¹H NMR (270 MHz, CDCl3): δ = 1.19 (6 H, d, J = 6.3 Hz), 3.52 (1 H, sept, J = 6.3 Hz), 4.26 (2 H, s), 7.77 (1 H, s). ¹³C NMR (68 MHz, CDCl3): δ = 23.3, 51.8, 59.8, 85.0, 155.3. IR (NaCl): ν = 1667 (C=N) cm-¹. MS (70 eV): m/z (%) = 201/203/205/207 (1) [M+], 186/188/190/192 (9), 124/126/128 (20), 116/118 (10), 111 (17), 96/98 (12), 70 (42), 63 (16), for chlorine isotopes, the reported relative intensity (%) represents the largest peak.

25

2-Chloromethyl-1-isopropylaziridine (15a)
Bp 40-43 ˚C (15 Torr). Purity: 90% (based on GC). ¹H NMR (270 MHz, CDCl3): δ = 1.12 (3 H, d, J = 6.3 Hz), 1.18 (3 H, d, J = 6.3 Hz), 1.40-1.46 (1 H, m), 1.73-1.75 (1 H, m), 1.46 (1 H, sept, J = 6.3 Hz), 1.68-1.74 (1 H, m), 3.31 (1 H, dd, J = 11.2, 7.6 Hz), 3.58 (1 H, dd, J = 11.2, 4.5 Hz). ¹³C NMR (68 MHz, CDCl3): δ = 21.8, 22.3, 33.3, 39.6, 47.2, 60.7. MS (70 eV): m/z (%) = 133/135 (3) [M+], 118/120 (10), 99 (15), 98 (69), 90/92 (15), 56 (100), 55 (10); for chlorine isotopes, the reported relative intensity (%) represents the largest peak.

30

N -(2,2,3-Trichloropropyl)isopropylamine (18a)
Bp 28.5 ˚C (0.2 Torr). ¹H NMR (270 MHz, CDCl3): δ = 1.07 (6 H, d, J = 6.3 Hz), 1.10-1.30 (1 H, m), 2.90 (1 H, sept, J = 6.3 Hz), 3.29 (2 H, s), 4.14 (2 H, s). ¹³C NMR (68 MHz, CDCl3): δ = 23.2, 48.8, 50.9, 56.6, 90.7. IR (NaCl): ν = 3330 (NH) cm-¹. MS (70 eV): m/z (%) = 203/205/207/209 (1) [M+], 188/190/192/194 (23), 72 (100). Anal. Calcd for C6H12Cl3N: C, 35.23; H, 5.91; N, 6.85. Found: C, 35.11; H, 6.09; N, 6.74; for chlorine isotopes, the reported relative intensity (%) represents the largest peak.

32

N -(2,2,3-Trichlorobutylidene)isopropylamine (21a)
¹H NMR (270 MHz, CDCl3): δ = 1.21 (6 H, d, J = 6.3 Hz), 1.78 (3 H, d, J = 6.5 Hz), 3.55 (1 H, sept, J = 6.3 Hz), 4.69 (1 H, q, J = 6.5 Hz), 7.78 (1 H, s). ¹³C NMR (68 MHz, CDCl3): δ = 20.5, 23.3, 23.4, 60.2, 62.3, 89.8, 156.6. IR (NaCl): ν = 1663 (C=N) cm-¹. MS (70 eV): m/z (%) = 215/217/219/221 (2) [M+], 57 (100), 56 (3); for chlorine isotopes, the reported relative intensity (%) represents the largest peak.

35

N -(2,2,3-Trichlorobutyl)- tert -butylamine (22a)
¹H NMR (270 MHz, CDCl3): δ = 1.11 (9 H, s), 1.55 (1 H, br s), 1.76 (3 H, d, J = 6.5 Hz), 3.26 and 3.44 (2 × 1 H, 2 d, J = 13.2 Hz), 4.75 (1 H, q, J = 6.5 Hz). ¹³C NMR (68 MHz, CDCl3): δ = 20.2, 29.3, 50.6, 55.1, 60.5, 96.4. IR (NaCl): ν = 3330 (NH) cm-¹. MS (70 eV): m/z (%), no [M+] = 216/218/220/222 (61), 181/183/185 (15), 140/142/144 (11), 118/120 (17), 87 (13), 86 (100), 70 (14), 58 (45), 57 (45), 53 (11). Anal. Calcd for C8H16Cl3N: C, 41.31; H, 6.93; N, 6.02. Found: C, 41.47; H, 7.13; N, 5.92; for chlorine isotopes, the reported relative intensity (%) represents the largest peak.