Head,Tail Hydroxylated Nylons Derived from D-Glucose
J . Org. Chem., Vol. 61, No. 17, 1996 5851
Hz), 4.24 (d, 1H), 3.25 (t, 2H, J ) 6.6 Hz), 2.68 (t, 2H, J ) 7.2
Hz), 1.48 (m, 4H), 1.32 (s, 8H). Anal. Calcd for C14H27O7N2-
Na (358.4): C, 46.92; H, 7.60; N, 7.82; Na, 6.41. Found: C,
46.70; H, 7.55; N, 7.78; Na, 6.46.
h ea d ,ta il-P oly(t et r a m et h ylen e D-glu ca r a m id e) (10b )
was prepared according to the method for 4a : salt 8b (1.00 g,
3.31 mmol), methanol (10 mL), cooled (ice bath), acetyl chloride
(1.5 mL, 20 mmol), room temperature 3 h, workup. head,tail-
Poly(tetramethylene-D-glucaramide) (11b, 0.749 g, 2.85 mmol,
86.3%): mp 185-188 °C dec; IR (KBr) 3312, 2940, 1635,
Sod iu m sa lt of 6-[N-(10′-Am in od ecyl)]-D-glu ca r a m id e
(8e) was prepared according to the method for 8a : salt 7 (1.00
g, 4.67 mmol), methanol (30 mL), decamethylenediamine (5.00
g, 29.0 mmol), reflux 3 h, oil bath temperature 95 °C. Sodium
salt of 6-[N-(10′-aminodecyl)]-D-glucaramide (8e, 1.63 g, 4.22
mmol, 90.3%): mp 195-198 °C; IR (KBr) 3391, 3165,1653,
and1543 cm-1 1H NMR (D2O) δ 4.32 (d, 1H, J ) 2.87 Hz),
;
4.09 (dd, 1H, J ) 4.53 Hz), 3.96 (dd, 1H, J ) 5.23 Hz), 3.30 (s,
4H) and 1.59 (s, 4H). Anal. Calcd for C10H18O6N2 (262.26):
C, 45.80; H, 6.92; N, 10.68. Found: C, 45.72; H, 6.94; N, 10.42.
h ea d ,ta il-P oly(h exa m eth ylen e D-glu ca r a m id e) (10c)
was prepared according to the method for 4a : salt 8c (1.00 g,
3.03 mmol), methanol (10 mL), cooled (ice bath), acetyl chloride
(1.5 mL, 20 mmol), room temperature 3 h, workup. head,tail-
Poly(hexamethylene-D-glucaramide) (4c, 0.802 g, 2.76 mmol,
91.3%): mp 187-190 °C dec; IR (KBr) 3313, 2931, 1637, and
1544 cm-1; 1H NMR (CF3COOD). δ 4.95 (s, 1H), 4.75 (s, 1H),
4.60 (d, 1H, 4.90 (d, 1H), 3.58 (s, 4H), 1.78 (s, 4H), 1.50 (s,
4H). Anal. Calcd for C12H22O6N2 (290.31): C, 49.65; H, 7.64;
N, 9.65. Found: C, 48.71; H, 7.41; N, 9.56.
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1628, and 1518 cm-1; H NMR (D2O) δ 4.14 (d, 1H, J ) 3.18
Hz), 4.06 (t, 1H), 3.97 (t, 1H, J ) 5.36 Hz), 4.24 (d, 1H), 3.24
(t, 2H, J ) 6.77 Hz), 2.69 (t, 2H, J ) 7.10 Hz), 1.50 (m, 4H),
1.30 (s, 12H). Anal. Calcd for C16H31O7N2Na (386.46): C,
49.73; H, 8.10; N, 7.25; Na, 5.95. Found: C, 49.45; H, 7.96;
N, 7.23; Na, 5.99.
Sod iu m sa lt of 6-[N-(12′-a m in od od ecyl)]-D-glu ca r a -
m id e (8f) was prepared according to the method for 8a : salt
7 (1.00 g, 4.67 mmol), methanol (30 mL), dodecamethylene-
diamine (5.0 g, 25.0 mmol), reflux 3 h, oil bath temperature
95 °C. Sodium salt 6-[N-(12′-aminododecyl)]-D-glucaramide
(8f, 1.77 g, 4.27 mmol, 91.5%): mp 198-200 °C; IR (KBr) 3390,
3338, 3163, 1653, 1630, and 1520 cm-1; 1H NMR (acetic acid-
d6) δ 4.52 (d, 1H, J ) 2.40 Hz), 4.32 (dd, 1H, J ) 3.12 Hz),
4.15 (dd, 1H, J ) 5.90 Hz), 4.35 (d, 1H), 3.30 (t, 2H), 3.04 (t,
2H), 1.69 (m, 2H), 1.55 (m, 2H), 1.32 (s, 16H). Anal. Calcd
for C18H35O7N2Na (414.5): C, 52.15; H, 8.52; N, 6.76; Na, 5.55.
Found: C, 52.20; H, 8.50; N, 6.72; Na, 5.55.
h ea d ,ta il-P oly(octa m eth ylen e D-glu ca r a m id e) (10d )
was prepared according to the method for 4a : salt 8d (1.00 g,
3.03 mmol), methanol (10 mL), cooled (ice bath), acetyl chloride
(1.5 mL, 20 mmol), room temperature 3 h, workup. head,tail-
Poly(octamethylene-D-glucaramide) (4d , 0.761 g, 2.39 mmol,
85.7%): mp 185-190 °C dec; IR (KBr) 3304, 2926, 1639, and
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1544 cm-1; H NMR (CF3COOD) δ 4.97 (s, 1H), 4.77 (s, 1H),
4.60 (d, 1H, J ) 5.7 Hz), 4.91 (d, 1H), 3.58 (s, 4H), 1.78 (s,
4H), 1.50 (s, 8H). Anal. Calcd for C14H26O6N2 (318.36): C,
52.82; H, 8.23; N, 8.80. Found: C, 49.14; H, 7.95; N, 8.65.
h ea d ,ta il-P oly(d eca m eth ylen e D-glu ca r a m id e) (10e)
was prepared according to the method for 4a : salt 8e (0.50 g,
1.29 mmol), methanol (10 mL), cooled (ice bath), acetyl chloride
(1.5 mL, 20 mmol), room temperature 3 h, workup. head,tail-
Poly(decamethylene-D-glucaramide) (4e, 0.370, 1.07 mmol,
82.5%): mp 193-196 °C dec; IR (KBr) 3305, 2923, 1640, and
h ea d ,ta il-P oly(eth ylen e D-glu ca r a m id e) (10a ). A mix-
ture of sodium salt of 6-[N-(2′-aminoethyl)]-D-glucaramide (8a ,
1.00 g, 3.65 mmol) and methanol (10 mL) in a 100 mL round-
bottomed flask was cooled in an ice bath, and to the mixture
was added acetyl chloride (1.5 mL, 20 mmol) with stirring to
dissolve the monoamide salt. The solution was stirred at room
temperature for 3 h and then concentrated to a syrup. The
1H NMR (D2O) spectral data from the syrup was consistent
with a mixture the of the C-1 methyl ester salt (9a ) and 1,4-
lactone salt (9b): for 9b, δ 5.13 (dd, 1H, J ) 3.69 Hz), 4.82 (d,
1H, J ) 8.94 Hz), 4.73 (d, 1H, J ) 3.69), 4.63 (dd, 1H, J )
7.91 Hz, J ) 8.94); for 9a , 4.55 (d, 1H, J ) 3.02 Hz), 4.31 (d,
1H, J ) 4.88 Hz), 4.14 (dd, 1H, J ) 5.26 Hz, J ) 3.02 Hz),
3.96 (dd, 1H, J ) 5.26 Hz, J ) 4.88 Hz), 3.82 (s, 3H), 3.18 (q,
2H). The molar ratio of 9b to 9a was estimated to be 1.6:1.0.
The syrup was dissolved in methanol (15 mL) and made just
basic by careful addition of triethylamine (pH paper). Ad-
ditional triethylamine (0.5 mL) was added to the solution
which was then stirred at room temperature for 30 min. The
insoluble solid product was removed by centrifugation, washed
with methanol (2 × 5 mL) and acetone (2 × 5 mL), and dried
at reduced pressure and at an oil bath temperature of 70 °C.
head,tail-Poly(ethylene-D-glucaramide) (4a, 0.753 g, 3.22 mmol,
88.2%): mp 185 °C dec; IR (KBr) 3343, 2950, 1651, and 1545
1
1546 cm-1; H NMR (CF3COOD) δ 4.93 (s, 1H), 4.75 (s, 1H),
4.58 (d, 1H, J ) 5.7 Hz), 4.88 (d, 1H), 3.58 (s, 4H), 1.71 (s,
4H), 1.41 (s, 12H). Anal. Calcd for C16H30O6N2 (346.43): C,
55.47; H, 8.73; N, 7.48. Found: C, 56.43; H, 8.94; N, 7.28.
h ea d ,ta il-P oly(d od eca m eth ylen e D-glu ca r a m id e) (10f)
was prepared according to the method for 4a : salt 8f (0.50g,
1.21 mmol), methanol (10 mL), cooled (ice bath), acetyl chloride
(1.5 mL, 20 mmol), room temperature 3 h, workup. head,tail-
Poly(dodecamethylene-D-glucaramide) (4f, 0.386, 1.03 mmol,
85.5%): mp 193-196 °C dec; IR (KBr) 3300 cm-1 (O-H,
1
stretch), 2921, 1641, and 1547 cm-1; H NMR (CF3COOD) δ
4.94 (s, 1H), 4.75 (s, 1H), 4.58 (d, 1H, J ) 6.0 Hz), 4.90 (d,
1H), 3.58 (s, 4H), 1.71 (s, 4H), 1.45 (s, 16 H). Anal. Calcd for
C18H34O6N2 (374.48): C, 57.33; H, 9.15; N, 7.48. Found: C,
56.88; H, 9.16; N, 7.46.
Ack n ow led gm en t. The authors acknowledge the
support of a UAB graduate Fellowship for L. Chen and
additional support from the Dilling Corporation.
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cm-1; H NMR (D2O) δ 4.34 (d, 1H, J ) 2.3 Hz), 4.10 (s, 1H),
3.96 (m, 1H, J ) 5.77 Hz), 4.26 (d, 1H), and 3.43 (s, 4H). Anal.
Calcd for C8H14O6N2 (234.21): C, 41.03; H 6.02; N, 11.96.
Found: C, 37.94; H, 5.83; N, 10.84.
J O960201E