Rapid Communications
J. Agric. Food Chem., Vol. 45, No. 1, 1997 5
Ta ble 1. P h ysicoch em ica l Da ta for th e Ca r ba m a tes 7-17 a n d th e Bis(ca r ba m a tes) 18-20
compd
MW
mp (°C)
NMR data
1
1
7
231.29
syrup liquid
H δ 4.05 (d, 2H, H-1-1′); 3.97 (dd, 1H, J 2,3′ ) 6.3 Hz, H-3); 3.68 (dd, 1H, J 3,3′ ) 8.3 Hz, H-3′);
4
.22 (m, 1H, J 2,3 ) 6.4 Hz, H-2); 1.29 (s, 3H, CH3); 1.03 (s, 3H, CH3); 3.19 (q, 4H, NCH2); 1.03
(
2
1
t, 6H, J CH2,CH3 ) 7.1 Hz, CH3); 13C δ 64.9 (1C C1); 66.2 (1C C3); 74.0 (1C C2); 109.4 (1C Ciso);
6.5 (1C CH3); 25.2 (1C CH3); 155.4 (1C CO); 41.7 (1C NCH2); 41.2 (1C NCH2); 13.9 (1C CH3);
3.4 (1C CH3)
8
9
331.41
syrup liquid
H δ 4.15 (dd, 1H, J 1,2 ) 5.3 Hz, H-1); 4.06 (m, 2H, J 1′,2 ) 4.1 Hz, J 1,1′ ) 13.4 Hz, H-1′-2);
3
4
.94 (dd, 1H, J 5,5′ ) 8.1 Hz, H-5); 3.74 (dd, 1H, J 4,5′ ) 6.7 Hz, H-5′); 3.77 (m, 1H, H-3);
.02 (m, 1H,
J 4,5 ) 6.7 Hz, H-4); 1.30 (s, 9H, CH3); 1.24 (s, 9H, CH3); 3.16 (q, 4H, J CH2,CH3 ) 7.1 Hz,
NCH2); 1.00 (t, 6H, CH3); 13C δ 64.3 (1C C1); 65.5 (1C C5); 75.7 (1C C2); 77.4 (1C C3);
7
2
5.0 (1C C4); 109.7 (1C Ciso); 109.6 (1C Ciso); 27.0 (1C CH3); 26.8 (1C CH3); 26.0 (1C CH3);
5.4 (1C CH3); 155.3 (1C CO); 41.7 (1C NCH2); 41.2 (1C NCH2); 13.9 (1C CH3); 13.3 (1C CH3)
1
1
1
247.36
261.34
347.48
syrup liquid
syrup liquid
42-43
H δ 4.05 (dd, 1H, J 1,2 ) 4.5 Hz, H-1); 4.00 (dd, 1H, J 1,1′ ) 11.5 Hz, J 1′,2 ) 5.3 Hz, H-1′);
3
.69 (dd, 1H, J 2,3′ ) 6.3 Hz, H-3); 3.39 (dd, 1H, J 3,3′ ) 8.3 Hz, H-3′); 4.09 (m, 1H, J 2,3 ) 6.5
Hz, H-2); 1.01 (s, 3H, CH3); 0.94 (s, 3H, CH3); 3.41(q, 2H, NCH2); 3.12 (q, 2H, NCH2);
0
6
4
.83 (t, 3, J CH2,CH3 ) 7.2 Hz, CH3); 0.80 (t, 3, J CH2,CH3 ) 7.2 Hz, CH3); 13C δ 70.9 (1C C1);
6.0 (1C C3); 73.6 (1C C2); 109.5 (1C Ciso); 26.9 (1C CH3); 25.4 (1C CH3); 186.8 (1C CS);
7.7 (1C NCH2); 43.3 (1C NCH2); 13.2 (1C CH3); 11.7 (1C CH3)
1
1
0
1
H δ 4.55 (dd, 1H, J 1,1′ ) 11.3 Hz, H-1); 4.46 (dd, 1H, J 1,2 ) 4.0 Hz, J 1′,2 ) 5.5 Hz, H-1′);
4
4
.03 (m, 1H, H-3); 3.73 (m 1H, H-3′); 4.38 (m, 1H, H-2); 1.39 (s 3H, CH3); 1.32 (s 3H, CH3);
.03 (m, 2H, J ) 7.3 Hz, NCH2); 3.73 (m, 4H, J ) 7.0 Hz, NCH2-OCH2); 3.62 (t, 2H,
1
3
J ) 7.0 Hz, OCH2); C δ 71.4 (1C C1); 66.0 (1C C3); 73.6 (1C C2); 109.7 (1C Ciso); 26.6
1C CH3); 25.1 (1C CH3); 187.4 (1C CS); 66.2 (1C OCH2); 66.0 (1C OCH2); 49.7 (1C NCH2);
5.8 (1C NCH2)
H δ 4.55 (dd, 1H, J 1,2 ) 6.7 Hz, H-1); 4.45 (dd, 1H, J 1′,2 ) 7.9 Hz, J 1,1′ ) 8.0 Hz, H-1′);
.97 (dd, 1H, J 5,5′ ) 11.9 Hz, H-5); 3.78 (dd, 1H, J 4,5′ ) 5.4 Hz, H-5′); 4.16 (m, 1H, J 2,3 ) 7.8
(
4
3
Hz, H-2); 3.80 (dd, 1H, J 3,4 ) 5.9 Hz, H-3); 4.09 (m, 1H, J 4,5 ) 3.3 Hz, H-4); 1.01 (s, 6H,
CH3); 0.94 (s, 6H, CH3); 3.71 (q, 2H, J CH2,CH3 ) 6.9 Hz, NCH2); 3.41 (q, 2H, J CH2,CH3 ) 6.9
Hz, NCH2); 1.13 (t, 3H, CH3); 1.09 (t, 3H, CH3); 13C δ 70.1 (1C C1); 65.6 (1C C5); 74.9
(
(
1C C2); 77.1 (1C C3); 75.5 (1C C4); 109.8 (1C Ciso); 109.6 (1C Ciso); 27.1 (1C CH3); 26.8
1C CH3); 26.1 (1C CH3); 25.4 (1C CH3); 186.7 (1C CS); 47.7 (1C NCH2); 43.3 (1C NCH2);
1
3.2 (1C CH3); 11.7 (1C CH3)
H δ 3.98 (dd, 1H, J 1,1′ ) 10.9 Hz, J 1,2 ) 4.7 Hz, H-1); 3.87 (dd, 1H, J 1′,2 ) 5.9 Hz, H-1′);
.35 (t, 2H, J 3,3′ ) 5.7 Hz, H-3-3′); 3.62 (m, 1H, J 2,3 ) 5.3 Hz, J 2,3′ ) 5.6 Hz, H-2); 3.20
q, 4H, J CH2,CH3 ) 7.1 Hz, NCH2); 1.03 (t, 6H, CH3); 13C δ 66.0 (1C C1); 62.6 (1C C3);
3.0 (1C C2); 155.0 (1C CO); 40.9 (2C NCH2); 13.4 (2C CH3)
1
1
1
1
2
3
191.23
251.28
syrup liquid
syrup liquid
3
(
7
H δ 4.01 (dd, 1H, J 1,1′ ) 11.0 Hz, J 1,2 ) 4.7 Hz, H-1); 3.95 (dd, 1H, J 1′,2 ) 6.6 Hz, H-1′);
3
4
.45 (s, 2H, H-5-5′); 3.73 (m, 1H, H-2); 3.51 (m, 1H, H-3); 3.37 (m, 1H, H-4); 3.19 (q,
H, J CH2,CH3 ) 7.0 Hz, NCH2); 1.03 (t 6H, CH3); 13C δ 66.2 (1C C1); 62.4 (1C C5); 69.7
(1C C2); 71.8 (1C C3); 70.3 (1C C4); 155.0 (1C CO); 40.7 (2C NCH2); 13.9 (1C CH3); 13.3
1C CH3)
(
1
1
4
207.29
syrup liquid
H δ 4.56 (dd, 1H, J 1,1′ ) 11.6 Hz, J 1,2 ) 5.3 Hz, H-1); 4.49 (dd, 1H, J 1′,2 ) 5.7 Hz, H-1′);
.64 (dd, 1H, J 3,3′ ) 11.6 Hz, J 2,3 ) 3.5 Hz, H-3); 3.54 (dd, 1H, J 2,3′ 5.6 Hz, H-3′); 3.94
m, 1H, H-2); 3.75 (q 2H, J CH2,CH3 ) 7.1 Hz, NCH2); 3.43 (q, 2H, J CH2,CH3 ) 7.1 Hz, NCH2);
.17 (t, 3H, CH3); 1.12 (t, 3H, CH3); 13C δ 70.8 (1C C1); 63.1 (1C C3); 70.5 (1C C2); 187.1
1C CS); 48.0 (1C NCH2); 43.5 (1C NCH2); 13.2 (1C CH3), 11.8 (1C CH3)
H δ 4.39 (dd, 1H, J 1,1′ ) 10.8 Hz, H-1); 4.23 (dd, 1H, J 1,2 ) 3.9 Hz, J 1′,2 ) 6.2 Hz, H-1′);
.37 (m, 2H, H-3-3′); 3.79 (m, 1H, H-2); 3.94 (m, 2H, NCH2); 3.73 (m, 2H, NCH2); 3.63
t, 2H, OCH2); 3.59 (t, 2H, OCH2); 13C δ 72.8 (1C C1); 62.5 (1C C3); 69.1 (1C C2); 187.1
1C CS); 65.5 (1C OCH2); 66.3 (1C OCH2); 49.1 (1C NCH2); 45.4 (1C NCH2)
H δ 4.36 (dd, 1H, J 1,1′ ) 11.0 Hz, J 1,2 ) 4.2 Hz, H-1); 4.28 (dd, 1H, J 1′,2 ) 6.6 Hz, H-1′);
.37 (s, 2H, H-5-5′); 3.84 (m, 1H, H-2); 3.50 (m, 1H, H-3); 3.47 (m, 1H, H-4); 3.72 (q, 2H,
J CH2,CH3 ) 7.1 Hz, NCH2); 3.50 (q, 2H, J CH2,CH3 ) 7.1 Hz, NCH2); 1.13 (t, 3H, CH3); 1.10
3
(
1
(
1
1
1
1
5
6
221.28
267.34
syrup liquid
3
(
(
65-68
3
1
3
(
1
t, 3H, CH3); C δ 72.4 (1C C1); 62.5 (1C C5); 69.5 (1C C2); 71.7 (1C C3); 70.5 (1C C4);
86.3 (1C CS); 46.8 (1C NCH2); 42.8 (1C NCH2); 13.1 (1C CH3), 11.6 (1C CH3)
H δ 3.46 (dd, 1H, J 1,1′ ) 9.6 Hz, J 1,2 ) 5.3 Hz, H-1); 3.38 (1H, J 1′,2 ) 2.5 Hz, H-1′); 3.34
1
1
7
223.36
syrup liquid
(
2
1
1H, J 3,3′ ) 13.2 Hz, H-3); 3.17 (dd, 1H, J 2,3′ ) 7.8 Hz, H-3′); 3.66 (m, 1H, H-2); 3.94 (q,
H, J CH2,CH3 ) 7.1 Hz, NCH2); 3.74 (q, 2H, J CH2,CH3 ) 7.1 Hz, NCH2); 1.19 (t, 3H, CH3);
.17 (t, 3H, CH3); 13C δ 40.8 (1C C1); 69.8 (1C C3); 64.9 (1C C2); 194.5 (1C CS); 48.9 (1C
NCH2); 46.3 (1C NCH2); 12.2 (1C CH3); 11.3 (1C CH3)
1
1
1
1
8
9
290.36
322.49
syrup liquid
syrup liquid
H δ 3.99 (d, 4H, H-1-1′-3-3′); 3.90 (m, 1H, H-2); 3.11 (2q, 8H, J CH2,CH3 ) 7.1 Hz, NCH2);
0
4
.95 (t, 12H, J CH2,CH3 ) 7.1 Hz, CH3); 13C δ 66.1 (2C C1-3); 68.7 (1C C2); 155.9 (2C CO);
1.7 (2C NCH2); 41.2 (2C NCH2); 13.8 (2C CH3); 13.2 (2C CH3)
H δ 4.48 (dd, 2H, J 1,1′, J 3,3′ ) 11.3 Hz, H-1-3); 4.43 (dd, 2H, J 1,2, J 2,3 ) 4.6 Hz, H-1′-3′);
4
.14 (m, 1H, J 1′,2, J 2,3′ ) 5.5 Hz, H-2); 3.67 (q, 4H, J CH2,CH3 ) 7.1 Hz, NCH2); 3.37 (q 4H,
1
3
J CH2,CH3 ) 7.1 Hz, NCH2); 1.09 (t, 6H, CH3); 1.07 (t 6H, CH3); C δ 70.3 (2C C1-3); 67.7
1C C2); 186.0 (2C CS); 46.9 (2C NCH2); 42.5 (2C NCH2); 12.3 (2C CH3); 10.8 (2C CH3)
H δ 3.68 (dd, 2H, J 1,1′, J 3,3′ ) 11.6 Hz, H-1-3); 3.61 (dd, 2H, J 1,2, J 2,3 ) 4.6 Hz, H-1′-3′);
.28 (m, 1H, J 1′,2, J 2,3′ ) 5.8 Hz, H-2); 4.07 (4H, NCH2); 3.76 (8H, NCH2-CH2); 3.55 (4H,
(
1
2
0
350.46
syrup liquid
4
1
3
CH2); C δ 71.4 (2C C1-3); 68.8 (1C C2); 187.5 (2C CS); 49.9 (2C NCH2); 46.0 (2C NCH2);
6
3.3 (2C OCH2); 65.9 (2C OCH2)
using only DMSO. The five compounds 12-14, 16, and
7 having only one graft of carbamoyl group on glycerol
and xylitol had slight growth inhibition against the five
fungi tested at 50, 20, and 2 ppm. The six carbamic
esters 18-23 were found to lack significant antifungal
activity against P. herpotrichoides (slow fungus). On
the other hand, the biological results against P. herpo-
trichoides (fast fungus) showed that 20 was more
antifungal than the commercial carbamate I at 50 ppm
(inhibition percent: day 4, 45 vs 38; day 7, 41 vs 23;
day 14, 19 vs 20; day 21, 5 vs 0), and all of the
bis(carbamic esters) 18, 19, and 21-23 had medium
1