PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
1
(
(
-
C ¼ O), 1545 (C ¼ C). H NMR(499.74 MHz, CDCl ): 2.53 3.77%, S, 8.63% . Found: C 61.04%, H, 4.83%; N, 3.33%;
3
s, 3 H, -NCH ), 2.90 (s, 4 H, -NCH ), 3.73 (t, J ¼ 9.28, 4 H, S, 8.05%
3
2
NCH ), 7.84 (dd, J ¼ 7.32, 8.29, 2 H, H
), 7.92 (dd,
2-(2,3-dihydroxypropylamino)-3-(3-hydroxybutan-2-ylthio)
2
arom
13
J ¼ 6.35, 7.81, 2 H, H
). C NMR (125.66MHz, CDCl ): naphthalene-1,4-dione (15) was synthesized from 2-(2,3-
arom
3
21
d ¼ 44.28 (-NCH ), 50.52, 54.18 (-NCH ), 153.10, 149.25, dihydroxypropylamino)-3-chloronaphthalene-1,4-dione
(9)
3
2
1
1
(
46.73, 144.12, 137.10, 135.75, 133.34, 131.30, 130.34, 132.47, (0,1 g, 0.355 mmol) and 3-Mercapto-2-butanol (14) (0.037 g,
32.41, 131.30, 130.83, 131.20 (Carom, CH
), 180.55, 179.18 0.355 mmol) by use of the general procedure 1.
arom
þ
C ¼ O). MS [þESI]: m/z ¼ 455 [Mþ H] , C H F N O S
Red viscous oil. Yield: 0.098 g (71%). Rf: 0.43 [EtAc] IR
21 15 5 2 2
(
Mw ¼ 454.41g/mol) ¼ Calculated: C, 55.51%; H, 3.33%; (KBr): 3381 (sb, -NH, -OH), 2871, 2929, 2972 (-CH), 1719,
1
N,6.16%; S, 7.06% Found: C, 55.41%; H, 3.20%; N, 6.10%; 1655 (C ¼ O), 1555 (C ¼ C). H NMR (499.74 MHz, CDCl
):
), 2.74 (m,
), 5.26 (s, 1 H, >CH-OH),
was synthesized from 2,3-Dichloro-1,4- 7.20-7.64 (m, 4 H, Harom). C NMR (125.66 MHz, CDCl ):
), 52.19 (NCH ), 37.71(-SCH), 66.99
), 69.32 (>CHOH), 75.76 (-OCH), 131.42, 129.87,
127.78 (Carom, CH
),180.20, 179.80 (C¼O). MS [þESI]:
3
S, 8.12%
1.21-1.18 (d, 6 H, -CH
-(2,3-dihydroxypropylamino)-3-chloronaphthalene-1,4- 2 H,-SCH ), 4.08 (m, 2 H,-NCH
2
3 2
), 3.77 (m, 4 H,-OCH
2
2
2
1
13
dione (9)
3
Naphthoquinone (1) (1.0 g, 2.033 mmol) and 3-Amino-1,2- 12.66, 15.88 (-CH
propanediol (8) (0.40 g, 2.033 mmol) by use of the general (-OCH
procedure 1.
Red Solid. Yield: 1.135 g (81%). Mp.: 137-138 C. Rf: 0.47 m/z ¼ 352[M þ H] , C H NO S (Mw¼ 351.42 g/mol) ¼
3
2
2
arom
þ
ꢃ
17
21
5
[
EtAc]. IR (KBr): 3454 (-OH), 1644 (C ¼ O), 1575 (C ¼ C). Calculated: C, 58.10%; H, 6.02%;N, 3.99%, S, 9.12% Found:
1
H
NMR(499.74 MHz, CDCl ): 3.61 (m, 2 H,-NCH ), C 58.02%, H, 6.44%; N, 3.55%; S, 10.01%.
3 2
4
.13(m, 2 H,-OCH ), 6.36 (s, 1 H, >CH-OH),8.07-7.96 (d,
2-(2,3-dihydroxypropylamino)-3-(2-hydroxypropylthio)-
2
13
J ¼ 8.30, 2 H, H
), 7.67-7.54 (t, J ¼ 7.32, 2 H, Harom).
C
naphthalene-1,4-dione (17) was synthesized from 2-(2,3-
arom
2
1
NMR (125.66 MHz, CDCl ): 46.17 (-NCH ), 63.31 (-OCH ), dihydroxypropylamino()-3-chloronaphthalene-1,4-dione 9)
3
2
2
7
0.07 (>CHOH), 133.90, 131.54, 128.93, 125.86, 125.15 (0.1 g, 0.355 mmol) and 1-Mercapto-2-propanol (16)
(
Carom, CHarom), 179.50, 179.00 (C ¼ O). MS [þESI]: m/ (0.033 g, 0.355 mmol) by use of the general procedure 1.
-
z ¼ 280.0 [M-H] , C H ClNO (M, 281.69) ¼ Calculated:
Red viscous oil. Yield: 0.082 g (61%). Rf: 0.48 [EtAc]. IR
13
12
4
C, 55.43%; H, 4.29%; N, 4.97% Found: C 55.22%, H, 4.19%; (KBr): 3346 (-NH, -OH), 2929 (-CH), 1679 (C ¼ O), 1550
1
N, 4.90%.
(C ¼ C). H NMR (499.74 MHz, CDCl
): 1.20-1.51 (m, 3 H,
3
2
-(2,3-dihydroxypropylamino)-3-(6-hydroxyhexylthio)- -CH ), 2.52-2.55 (m, 2 H,-SCH ), 4.09-4.25 (m, 2 H,-OCH ),
3
2
2
naphthalene-1,4-dione (11) was synthesized from 2-(2,3- 3.54-3.57 (m, 2 H, -NCH ), 4.79 (s, 1 H, >CH-OH), 7.62-
2
dihydroxypropylamino)-3-chloronaphthalene-1,4-dione
7.66 (dd, J ¼ 8.78, 8.78, 2 H, H
), 7.67-7.54 (t, J ¼ 7.32,
arom
[
21]
13
(
9)
(0.1 g, 0.355 mmol) and 6-Merkapto-1-Hexanol (10) 2 H,
H
).
C
NMR (125.66 MHz, CDCl ): 46.68
3
arom
(
0.047 mL, 0.355 mmol) by use of the general procedure 1.
(-NCH ), 63.34 (-OCH ), 67.17 (>CHOH), 166.73, 133.88,
2
2
Red viscous oil. Yield: 0.086 g (89%). Rf: 0.65 [EtAc]. IR 131.47, 129.82, 127.79, 108.75 (Carom, CHarom), 180.51,
-
(
1
8
KBr): 3373 (-NH, -OH), 2856, 2930 (-CH), 1675 (C ¼ O), 179.04 (C ¼ O). MS [þESI]: m/z ¼ 371 [M þ Cl] ,
1
592 (C ¼ C). H NMR(499.74 MHz, CDCl ): 1.21-1.75 (m, C H NO S (Mw¼ 337.39 g/mol) Calculated: C, 56.96%; H,
3
16 19
5
H, -CH ), 3.55 (m, 4 H,-OCH ), 2.60 (t, J ¼ 7.32, 2 H,- 5.68%; N, 4.15%, S, 9.50% Found: C 56.90%, H, 5.60%; N,
2
2
SCH ), 3.65 (m, 2 H,-NCH ), 6.97 (s, 1 H, >CH-OH), 7.52- 4.22%; S, 10.02%.
2
2
13
8
2
6
1
.05 (m, 4 H, Harom). C NMR (125.66 MHz, CDCl ): 24.36,
2-(2,3-dihydroxypropylamino)-3-(4-fluorophenylthio)-
7.18, 27.23, 31.52 (-CH ), 46.94 (-NCH ), 33.85 (-SCH ), naphthalene-1,4-dione (19a) was synthesized from 2-(2,3-
1.73 (-OCH ), 70.09 (>CHOH), 159.18, 133.60, 131.11, dihydroxypropylamino)-3-chloronaphthalene-1,4-dione (9)
3
2
2
2
2
2
1
25.52, (Carom, CH
), 180.51, 179.04 (C ¼ O). MS [þESI]:
(0,065 g, 0.231 mmol) and 4-Fluorothiophenol (18a)
arom
-
m/z ¼ 378.0 [M-H] , C H NO S (M, 379.47) ¼ Calculated: (0.029 g, 0.231 mmol) by use of the general procedure 1.
19
25
5
C, 60.14%; H, 6.64%; N, 3.69%, S, 8.45% Found: C 60,11%,
H., 6.56%; N, 3.45%; S, 9.10%.
Red viscous oil. Yield: 0.63 g (86%). Rf: 0.37 [EtAc]. IR
(KBr): 3274 (-NH, -OH), 3019, 2937 (-CH), 1687 (C ¼ O),
1
2
-(2,3-dihydroxypropylamino)-3-(2-hydroxyphenylthio)- 1549 (C ¼ C). H NMR(499.74 MHz, CDCl ): 3.61- 3.66 (m,
3
naphthalene-1,4-dione (13) was synthesized from 2-(2,3- 2 H,-NCH ), 4.09-4.13(m, 2 H,-OCH ), 7.23-8.09 (m, 8 H,
2
13
2
21
dihydroxypropylamino)-3-chloronaphthalene-1,4-dione (9)
Harom). C NMR (125.66 MHz, CDCl ): 46.37 (-NCH ),
3 2
(
0.1 g, 0.355 mmol) and 2-Mercaptophenol (12a) (0.044 g, 63.28 (-OCH ), 69.72 (>CHOH), 134.08, 131.40, 126.13,
2
0
.355 mmol) by use of the general procedure 1.
Red Solid. Yield: 0.085 g (58%). Mp.: 153-154 C. Rf: 0.47 (C ¼ O). MS [þESI]: m/z ¼ 374 [M þ H] , C H FNO S
125.74, 115.33, 115.15 (Carom, CHarom), 180.07, 179.80
ꢃ
þ
1
9
16
4
[
1
EtAc]. IR (KBr): 3514 (-NH, -OH), 2853, 2920, 2948 (-CH), (M ¼ 373.40 g/mol) Calculated: C, 61.12%; H, 4.32%; N,
w
1
674 (C ¼ O). H NMR(499.74 MHz, CDCl ): 3.60 (m, 4 H,- 3.75%; S, 8.59%; Found: C 61.20%, H, 4.30%; N, 3.58%;
3
OCH ), 3.77 (m, 2 H,-NCH ), 6.92 (s, 1 H, >CH-OH), 7.56- S, 9.05%.
2
2
13
8
.09 (m, 8 H, Harom). C NMR (125.66 MHz, CDCl ): 45.86
2-(2,3-dihydroxypropylamino)-3-(4-bromophenylthio)-
3
(
1
-NCH ), 63.32 (-OCH ), 70.07 (>CHOH), 133.91, 133.90, naphthalene-1,4-dione (19 b) was synthesized from 2-(2,3-
2
2
21
31.54, 131.50, 125.85 (Carom, CHarom), 179.50, 179.05 dihydroxypropylamino)-3-chloronaphthalene-1,4-dione (9)
þ
(
(
C ¼ O). MS [þESI]: m/z ¼ 372 [M þ H] , C H NO S (0.065 g, 0.231 mmol) and 4-Bromothiophenol (18 b) (0.383 g,
1
9
17
5
Mw¼ 371.41 g/mol) ¼ Calculated: C, 61.44%; H, 4.61%; N, 0.231 mmol) by use of the general procedure 1.