6
438 J . Org. Chem., Vol. 62, No. 18, 1997
Notes
F igu r e 3. 1H NMR spectra of compound 4 from (a) reaction of 1 and 2 in a monolayer surface and (b) solution synthesis. A large
water peak appearing at a chemical shift of 1.5 ppm was present in both samples. Solvent peaks used in purification of the
monolayer derived sample are observed at 2.18 ppm (acetone), 3.5 (methanol).
CDCl
3
) δ 6.20 (s, 1H), 4.20 (d, 2H, J ) 8.92 Hz), 2.91 (t, 2H, J )
Hz). 13C NMR (100.614 MHz, CDCl
31.91, 29.68, 29.66, 29.64, 29.58, 29.54, 29.34, 29.31, 26.97, 22.67,
3
) δ 172.45, 44.80, 39.01,
1
2
1.56 Hz), 2.06 (s, 3H), 1.57 (quin, 2H, J ) 11.64 Hz), 1.25 (s,
1
3
6H), 0.87 (t, 3H, J ) 10.92 Hz).
) δ 196.91, 170.07, 49.26, 49.10, 33.92, 31.88, 29.64, 29.62,
9.59, 29.53, 29.41, 29.31, 29.04, 28.78, 28.70, 25.61, 24.91, 22.93,
C NMR (100.614 MHz,
-1
1
1
2 2
4.08. FT-IR (CH Cl , ν, cm ) 3319, 2918, 2850, 1687, 1641,
CDCl
3
557, 1459, 1407, 1368, 1316. FAB-HRMS (NBA/NaI-matrix)
2
2
1
+
calculated for [C18
N-Acetylglycyl-Glycin e Hexadecyl Am ide (4). To a stirred
solution of N-acetylglycine (76 mg, 0.65 mmol) in freshly distilled
H
38
N
2
O + Na] : 321.2882; found: 321.2888.
-
1
2.64, 14.06. FT-IR (CH
649, 1626, 1543, 1465, 1368. FAB-HRMS (NBA/NaI-matrix)
2 2
Cl , ν, cm ) 3285, 2917, 2843, 1679,
+
2
calculated for [C20H39NO S + Na] : 380.2599; found: 380.2609.
N-Car boben zyloxyglycin e Hexadecyl Am ide. To a stirred
solution of carbobenzyloxyglycine (300 mg, 1.45 mmol) in freshly
2 2
distilled CH Cl (15 mL) and pyridine (80.2 µL, 1.43 mmol) was
added hexadecylamine (362 mg, 1.5 mmol). The mixture was
cooled to 0 °C for 15 min followed by the addition of dicyclo-
hexylcarbodiimide (295.05 mg, 1.43 mmol). The reaction was
stirred at 0 °C for 1 h and then at room temperature for 2 h.
The mixture was stored overnight in a refrigerator to precipitate
2 2
CH Cl (10 mL) and dry pyridine (36 µL, 0.65 mmol) was added
glycine hexadecyl amide (200 mg, 0.67 mmol). The mixture was
cooled to 0 °C followed by the addition of dicyclohexylcarbodi-
imide (134 mg, 0.65 mmol). The reaction was stirred at 0 °C
for 1 h and then at room temperature for 2 h. The flask was
kept overnight in a refrigerator to precipitate urea. The reaction
was quenched by the addition of CH
removed by vacuum filtration and the residue washed repeatedly
with CH Cl . Solvents were removed under reduced pressure.
Flash column chromatography of the residue eluting with 5%
CH OH/2% acetone/CH Cl ) afforded 181 mg (70%) of a white
solid. H NMR (250 MHz, CDCl ) δ 6.58 (s, 1H), 6.16 (s, 1H),
.96 (s, 1H), 3.93 (dd, 4H, J ) 4.75 Hz, 4.08 Hz), 3.25 (q, 2H, J
3
COOH (1 mL). Urea was
2
2
urea. The reaction was quenched by the addition of CH
1 mL). Urea was removed by vacuum filtration and the residue
washed repeatedly with CH Cl The resulting solution was
washed with 5% HCl (2 × 15 mL), 5% NaHCO (2 × 15 mL),
SO
3
COOH
(
3
2
2
2
2
.
1
3
3
5
and brine (2 × 10 mL). The organic layer was dried over Na
2
4
)
6.4 Hz), 2.06 (s, 3H), 1.59 (quin, 2H, J ) 4.77), 1.25 (s, 26H),
and filtered, and solvent was removed under reduced pressure.
13
0
1
3
.87 (t, 3H, J ) 6.62 Hz). C NMR (100.614 MHz, CD
74.26, 172.32, 171.4, 44.00, 43.36, 40.49, 33.04, 30.75, 30.67,
0.42, 30.36, 27.93, 23.70, 22.44, 14.40, 10.08. FT-IR (CH Cl
3
OD) δ
The crude sample was subjected to flash column chromatography
1
(3% CH
3
OH/CH
2
Cl
2
) to give 470 mg (76%) of a white solid.
H
2
2
,
NMR (400 MHz, CDCl
3
) δ 7.36 (m, 5H), 5.87 (s, 1H), 5.34 (s,
-1
ν, cm ) 3280, 2918, 2845, 1730, 1634, 1544, 1459, 1419, 1374.
FAB-HRMS (NBA/NaI-matrix) calculated for [C22
Na] : 420.3202; found: 420.3200.
1
6
H), 5.13 (s, 2H), 3.83 (d, 2H, J ) 5.72 Hz), 3.24 (q, 2H, J )
.69 Hz), 1.48 (qu, 2H, J ) 6.64 Hz), 1.25 (s, 26H), 0.88 (t, 3H,
43 3 3
H N O +
+
1
3
J ) 7.04 Hz). C NMR (100.614 MHz, CDCl
1
2
3
) δ 168.59, 136.09,
28.58, 128.30, 128.13, 110.45, 67.26, 44.75, 39.62, 31.91, 29.68,
9.66, 29.64, 29.58, 29.52, 29.50, 29.35, 29.25, 26.84, 22.68, 14.10.
Ack n ow led gm en t. This work was supported in part
by the National Science Foundation under grant num-
ber MCB-9508066 and Brown University.
-
1
2 2
FT-IR (CH Cl , ν, cm ) 3333, 2911, 2844, 1688, 1638, 1527,
1
455, 1344, 1261. FAB-HRMS (NBA/NaI-matrix) calculated for
+
[C
26
H
44
N
2
O
3
+ Na] : 455.3249; found: 455.3251.
Glycin e Hexa d ecyl Am id e (2). A 50 mL, two-necked, round
bottom flask was charged with a solution of N-carbobenzylox-
yglycine hexadecyl amide (620 mg, 1.43 mmol) in CH Cl (10
mL) and CH OH (5 mL) and Pd(OH) /C (10 mg). The reaction
was stirred under H (1 atm) for 12 h. Catalyst was removed
Su p p or tin g In for m a tion Ava ila ble: Proton and carbon
NMR spectra, IR spectra, and mass spectra are available for
all compounds described in the Experimental Section (18
pages). This material is contained in libraries on microfiche,
immediately follows this article in the microfilm version of the
journal, and can be ordered from the ACS; see any current
masthead page for ordering.
2
2
3
2
2
by filtration through Celite. The solvents were evaporated to
give a white crystalline material. The desired product was
obtained in quantitative yield (427 mg). H NMR (400 MHz,
1
CDCl
3
) δ 7.22 (s, 1H), 3.34 (s, 2H), 3.27 (q, 2H, J ) 6.94 Hz),
1
.53 (quin, 2H, J ) 7.14 Hz), 1.25 (s, 26H), 0.88 (t, 3H, J ) 6.68
J O970510K