4842
J. Pernak et al. / Tetrahedron 67 (2011) 4838e4844
chloride was added and the mixture was stirred for 30 min at room
temperature. The product deposited as the bottom layer, which was
separated. Then it was dissolved in 50 mL of chloroform. The or-
ganic phase was washed with distilled water until no chloride was
present in water. After removal of chloroform the product was dried
under reduced pressure at 60 ꢀC for 24 h.
J¼7.3 Hz, 3H), 1.24 (sex, J¼7.4 Hz, 2H), 1.41 (d, J¼6.8 Hz, 3H), 1.72
(q, J¼5.5 Hz, 2H), 2.12 (s, 3H), 3.84 (s, 3H), 4.15 (t, J¼7.1 Hz, 2H), 4.24
(q, J¼6.7 Hz, 1H), 6.73 (d, J¼8.8 Hz, 1H), 7.02 (dd, J1,2¼2.6 Hz,
J1,3¼8.8 Hz, 1H), 7.10 (d, J¼2.7 Hz, 1H), 7.77 (d, J¼1.7 Hz, 1H), 7.84 (d,
J¼1.3 Hz, 1H), 9.65 (s, 1H); 13C NMR
d
ppm¼13.3, 16.0, 18.8, 19.3,
31.5, 35.6, 48.4, 76.0, 113.4, 122.2, 122.3, 123.6, 125.8, 127.8, 129.3,
137.2, 156.0, 173.9. Elemental analysis calcd (%) for C18H25ClN2O3
(M¼352.90) C 61.27, H 7.14, N 7.94; found: C 61.56, H 6.89, N 8.32.
4.2.1. Hydrogenated tallowtrimethylammonium (4-chloro-2-methyl-
phenoxy)acetate (N-1) (chain distribution C12
H
25d1, C14H29d4,
C16H33d31, C18H37d64%). 1H NMR (CDCl3)
d
ppm¼0.88 (t, J¼6.7 Hz,
4.2.8. 1-Dodecylpyridinium (2,4-dichlorophenoxy)acetate (Pyr-1).
3H), 1.26 (m, 28H), 1.59 (q, J¼7.3 Hz, 2H), 2.21 (s, 3H), 3.14 (s, 9H), 3.22
(t, J¼8.5 Hz, 2H), 4.34 (s, 2H), 6.71 (d, J¼8.6 Hz, 1H), 7.02 (dd,
J1,2¼2.5 Hz, J1,3¼8.8 Hz, 1H), 7.04 (d, J¼2.5 Hz, 1H); 13C NMR
1H NMR (CDCl3)
d
ppm¼0.87 (t, J¼6.7 Hz, 3H), 1.21 (m, 18H), 1.86 (q,
J¼7.7 Hz, 2H), 4.46 (s, 2H), 4.67 (t, J¼7.4 Hz, 2H), 6.87 (d, J¼8.8 Hz,
1H), 7.08 (dd, J1,2¼2.7 Hz, J1,3¼8.7 Hz, 1H), 7.24 (d, J¼2.5 Hz,1H), 8.00
(t, J¼7.1 Hz, 2H), 8.39 (t, J¼7.8 Hz,1H), 9.09 (t, J¼5.5 Hz, 2H); 13C NMR
d
ppm¼14.1, 16.4, 22.7, 23.1, 26.3, 29.32, 29.35, 29.52, 29.59, 29.66,
29.72, 31.9, 53.0, 66.6, 68.3, 112.7, 124.2, 126.1, 128.4, 129.9, 155.8, 173.4.
d
ppm¼14.1, 22.6, 26.1, 29.1, 29.3, 29.4, 29.51, 29.56, 31.6, 31.8, 61.9,
68.6, 114.5, 122.5, 124.8, 127.4, 128.1, 129.3, 144.7, 144.8, 153.2, 172.1.
Elemental analysis calcd (%) for C25H35O3NCl2 (M¼468.51): C 64.09,
H 7.54, N 2.99; found: C 63.98, H 7.82, N 3.11.
4.2.2. Di(hydrogenated tallow)dimethylammonium (4-chloro-2-
methylphenoxy)acetated(N-2) (chain distribution C12
H
25d1,
C14 29d4, C16 33d31, C18
H
H
H
37d64%). 1H NMR (CDCl3)
d
ppm¼0.88
(t, J¼6.7 Hz, 6H), 1.24 (m, 49H), 1.57 (q, J¼6.9 Hz, 4H), 2.23 (s, 3H),
3.21 (s, 6H), 3.28 (t, J¼8.5 Hz, 4H), 4.41 (s, 2H), 6.76 (d, J¼8.7 Hz,1H),
6.98 (dd, J1,2¼2.6 Hz, J1,3¼8.6 Hz, 1H), 7.03 (d, J¼2.6 Hz, 1H); 13C
4.2.9. 1-Dodecylpyridinium (4-chloro-2-methylphenoxy)acetate
(Pyr-2). 1H NMR (CDCl3)
d
ppm¼0.87 (t, J¼6.7 Hz, 3H), 1.24 (m,
18H), 1.92 (q, J¼7.4 Hz, 2H), 2.19 (s, 3H), 4.44 (s, 2H), 4.76 (t,
J¼7.4 Hz, 2H), 6.77 (d, J¼8.8 Hz, 1H), 6.99 (dd,
J1,2¼2.6 Hz, J1,3¼8.8 Hz, 1H), 7.01 (d, J¼2.6 Hz, 1H), 7.98 (t,
J¼7.1 Hz, 2H), 8.34 (t, J¼7.7 Hz, 1H), 9.35 (d, J¼5.8 Hz, 2H); 13C
NMR
d
ppm¼13.9, 16.3, 22.46, 22.50, 26.1, 29.0, 29.17, 29.20, 29.30,
29.41, 29.47, 29.51, 31.7, 50.6, 63.0, 68.8, 112.7, 123.7, 125.8, 128.2,
129.7, 156.2, 172.6.
NMR
d
ppm¼14.1, 16.4, 22.6, 26.1, 29.0, 29.24, 29.31, 29.44,
4.2.3. Didecyldimethylammonium (4-chloro-2-methylphenoxy)-
29.51, 31.8, 61.8, 68.7, 112.7, 123.9, 125.9, 128.0, 128.2, 129.7,
144.4, 145.1, 156.0, 173.2. Elemental analysis calcd (%) for
C26H38ClNO3 (M¼448.04): C 69.70, H 8.55, N 3.13; found C
69.95, H 8.82, N 2.98.
acetated(N-3). 1H NMR (CDCl3)
d
ppm¼0.88 (t, J¼6.7 Hz, 6H),
1.25 (m, 28H), 1.57 (q, J¼6.9 Hz, 4H), 2.24 (s, 3H), 3.12 (s, 6H), 3.21
(t, J¼8.5 Hz, 4H), 4.41 (s, 2H), 6.75 (d, J¼8.8 Hz, 1H), 7.00 (dd,
J1,2¼2.6 Hz, J1,3¼8.8 Hz, 1H), 7.04 (d, J¼2.6 Hz, 1H); 13C NMR
d
ppm¼14.0,16.3, 22.5, 22.52, 26.1, 29.06, 29.12, 29.26, 29.30, 31.7,
4.2.10. 1-Hexadecylpyridinium (4-chloro-2-methylphenoxy)ace-
51.1, 63.3, 68.4, 112.7, 124.1, 126.0, 128.4, 129.9, 156.1, 173.1. Ele-
mental analysis calcd (%) for C31H56ClNO3 (526.23): C 70.75, H
10.73, N 2.66; found: C 70.54, H 10.52, N 2.98.
tate (Pyr-3). 1H NMR (CDCl3)
d
ppm¼0.88 (t, J¼6.7 Hz, 3H), 1.25
(m, 26H), 1.88 (q, J¼6.6 Hz, 2H), 2.20 (s, 3H), 4.43 (s, 2H), 4.72 (t,
J¼7.4 Hz, 2H), 6.76 (d, J¼8.5 Hz, 1H), 7.00 (dd, J1,2¼2.6 Hz, J1,3¼8.6 Hz,
1H), 7.01 (d, J¼2.6,1H), 7.97 (t, J¼7.1 Hz, 2H), 8.33 (t, J¼7.8 Hz,1H), 9.26
4.2.4. Tetrabutylphosphonium (2,4-dichlorophenoxy)acetate (P-1).
(d, J¼5.5 Hz, 2H); 13C NMR
ppm¼14.1, 16.4, 22.7, 26.1, 29.03, 29.29,
d
1H NMR (CDCl3)
d
ppm¼0.95 (t, J¼7.0, 12H), 1.46 (m, 16H), 2.28 (m,
29.34, 29.48, 29.55, 29.59, 29.63, 31.8, 31.9, 61.9, 68.7, 112.7, 123.9,
125.9,128.0,128.2,129.8,144.4,145.0,156.0,173.2. Elemental analysis
calcd (%) for C30H46ClNO3 (M¼504.14): C 71.47, H 9.20, N 2.78; found C
71.05, H 8.98, N 2.48.
8H), 4.50 (s, 2H), 6.93 (d, J¼8.8 Hz, 1H), 7.08 (dd, J1,2¼2.7 Hz,
J1,3¼9.0 Hz, 1H), 7.28 (d, J¼2.5 Hz, 1H); 13C NMR
d
ppm¼13.2
(d, JCP¼1.0 Hz), 18.3 (d, JCP¼47.2 Hz), 23.4 (d, JCP¼9.0 Hz), 23.7 (d,
JCP¼15.5 Hz), 69.1, 114.8, 122.3, 124.1, 127.1, 129.0, 153.8, 171.3. Ele-
mental analysis calcd (%) for C24H41O3PCl2 (M¼479.52): C 60.11, H
8.64; found: C 60.31, H 8.43.
4.2.11. 1-Methy-1-propylpiperydinium (4-chloro-2-methylphenoxy)-
acetate (Pip-1). 1H NMR (DMSO-d6)
d
ppm¼0.90 (t, J¼7.3 Hz, 3H),
1.51 (sex, J¼5.8 Hz, 2H), 1.63 (q, J¼4.9 Hz, 2H), 1.70 (q, J¼5.0 Hz, 4H),
1.74 (t, J¼3.9 Hz, 4H), 2.16 (s, 3H), 2.99 (s, 3H), 3.29 (t, J¼6.0 Hz, 2H),
4.20 (s, 2H), 6.72 (d, J¼8.6 Hz, 1H), 7.08 (dd, J1,2¼2.6 Hz, J1,3¼8.6 Hz,
4.2.5. Tetrabutylphosphonium (4-chloro-2-methylphenoxy)ace-
tate (P-2). 1H NMR (CDCl3)
d
ppm¼0.95 (t, J¼5.8 Hz, 12H), 1.46
(m,16H), 2.25 (s, 3H), 2.28 (m, 8H), 4.44 (s, 2H), 6.78 (d, J¼8.5 Hz,1H),
1H), 7.13 (d, J¼2.6 Hz, 1H); 13C NMR
d
ppm¼10.7, 14.7, 16.1, 19.3,
7.03 (dd, J1,2¼2.6 Hz, J1,3¼8.6 Hz, 1H), 7.04 (d, J¼2.6 Hz, 1H); 13C NMR
20.8, 47.1, 59.9, 63.7, 68.2, 113.1, 122.7, 126.0, 128.0, 129.5, 156.2,
171.3. Elemental analysis calcd (%) for C18H28ClNO3 (M¼341.92): C
63.23, H 8.27, N 4.10; found C 63.62, H 8.01, N 4.32.
d
ppm¼13.1 (d, JCP¼1.0 Hz), 16.1, 18.5 (d, JCP¼47.5 Hz), 23.4 (d,
JCP¼4.8 Hz), 23.7, (d, JCP¼15.2), 68.5, 112.7, 123.6, 125.6, 128.2, 129.5,
156.1,172.3. Elemental analysis calcd (%) for C25H44O3PCl (M¼459.11):
C 65.40, H 9.68; found: C 65.21, H 9.75.
4.2.12. 4-Butyl-4-methylmorpholinium (4-chloro-2-methylphenoxy)-
acetate (Mor-1). 1H NMR (DMSO-d6)
d
ppm¼0.94 (t, J¼7.3 Hz, 3H),
4.2.6. Tetraoctylphosphonium (þ)e(R)-2-(4-chloro-2-methylphenoxy)-
1.32 (sex, J¼7.3 Hz, 2H), 1.65 (q, J¼4.1 Hz, 2H), 2.16 (s, 3H), 3.14 (s,
3H), 3.42 (t, J¼4.4 Hz, 2H), 3.48 (t, J¼7.6 Hz, 4H), 3.91 (t, J¼4.5 Hz,
4H), 4.21 (s, 2H), 6.72 (d, J¼8.8 Hz, 1H), 7.08 (dd, J1,2¼2.8 Hz,
propionated(P-3). 1H NMR (CDCl3)
d
ppm¼0.88 (t, J¼6.6 Hz, 12H),
1.27 (m, 40H), 1.42 (q, J¼5.6 Hz, 8H), 1.60 (d, J¼6.9 Hz, 3H), 2.20 (t,
J¼2.7 Hz, 8H), 2.24 (s, 3H), 4.42 (q, J¼6.7 Hz,1H), 6.83 (d, J¼8.8 Hz,1H),
6.97 (dd, J1,2¼2.7 Hz, J1,3¼8.7 Hz, 1H), 7.02 (d, J¼2.7 Hz, 1H); 13C NMR
J1,3¼8.8 Hz, 1H), 7.14 (d, J¼2.8 Hz, 1H); 13C NMR
d
ppm¼13.6, 16.1,
19.3, 22.8, 46.0, 58.9, 59.8, 63.5, 68.2, 112.9, 122.6, 125.8, 127.8, 129.3,
155.9, 171.1. Elemental analysis calcd (%) for C18H28ClNO4
(M¼357.92): C 60.40, H 7.90, N 3.91; found C 60.12, H 8.05, N 4.01.
d
ppm¼13.8, 16.3, 18.3, 18.9, 19.4, 21.6 (d, JCP¼4.8 Hz), 22.3, 28.7, 30.6
(d, JCP¼14.5), 31.4, 76.5, 113.3, 123.3, 125.7, 128.1, 129.5, 156.0, 176.3.
Elemental analysis calcd (%) for C42H78ClO3P (M¼697.62) C 72.32, H
11.27; found: C 72.48, H 11.07.
4.2.13. (2-Chloroethyl)trimethylammonium (4-chloro-2-methyl-
phenoxy)acetate (N-4). Preparation: 0.01 mol of (4-chloro-2-
methylphenoxy)acetic acid, 30 mL of distilled water and
0.01 mol of NaOH were placed in round-bottom flask. The
4.2.7. 3-Butyl-1-methylimidazolium (þ)-(R)-2-(4-chloro-2-methyl-
phenoxy)propionated(IM-1). 1H NMR (DMSO-d6)
d
ppm¼0.88 (t,