Diamondoid Phosphines – Selective Phosphorylation of Nanodiamonds
456.2341, calcd. for C28H38ClOP: 456.2349; anal. calcd. for
C28H38ClOP (457.03): C 73.58, H 8.38; found: C 73.31, H
8.40.
washed with distilled water (100 mL) and dried over
Na2SO4. Purification was achieved by column chromatogra-
phy on silica gel (CH2Cl2, Rf: 0.71); yield: 175 mg
(0.34 mmol, 89%); mp 215–2358C; 1H NMR (600 MHz,
CDCl3): d=2.77 (d, J=209.3 Hz, 1H, P-H), 1.93–1.73 (m,
10H, H-8,10,15), 1.72–1.56 (m, 24H, H-3,4,5,6,7,11,13,14,18),
Di-9-triamantylphosphinic Acid Chloride (8)
Compound 3 (1 g, 4.2 mmol), AlCl3 (2 g, 15 mmol), and PCl3
(0.18 mL, 2.1 mmol) in dry CH2Cl2 (20 mL) were refluxed
for 4.5 h, stirred at room temperature for 15 h and refluxed
again for 8.5 h. The reaction mixture was quenched with
10% HCl solution (100 mL) and CH2Cl2 (50 mL). After
phase separation the aqueous phase was extracted with
CH2Cl2 (2ꢃ50 mL), combined organic phases were washed
with distilled water (100 mL) and dried over Na2SO4. Purifi-
cation was achieved by column chromatography on silica gel
(CH2Cl2:ether 9:1, Rf: 0.40); yield: 742 mg (1.32 mmol,
63%); mp 280–2848C; 1H NMR (400 MHz, CDCl3): d=
2.18–2.04 (m, 8H, H-8,10), 1.88 (br s, 2H, H-15), 1.83 (br s,
4H, H-7,11), 1.77–1.63 (m, 24H, H-3,4,5,6,13,14,17,18), 1.51
(br s, 4H, H-2,12), 1.36–1.30 (m, 4H, H-16); 13C NMR
1.46–1.31 (m, 8H, H-2,12,17), 1.26–1.21 (m, 4H, H-16);
2
13C NMR (100 MHz, CDCl3): d=51.2 [d, J
A
C-17], 46.0 (C-2,12), 45.2 (C-16), 44.0 [d, 2J
10.1 Hz, C-8,10], 38.6 [d, 3J(13C,31P)=9.1 Hz, C-7,11], 38.1
(C-5), 38.0 (C-14,18), 37.8 (C-3,13), 35.0 (C-4), 34.3 (C-6),
(13C,31P)=
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
34.2 [d, 2J(13C,31P)=8.0 Hz, C-1], 33.6 [d, 1J(13C,31P)=
ACTHNUTRGENNUG CAHTUNGTRENNUGN
15.1 Hz, C-9], 27.8 (C-15); 31P NMR (162 MHz, CDCl3,
H3PO4 external standard): d=13.43; IR (KBr): n=2904,
2870, 2269, 1441, 1338, 1305, 1245, 1055, 1003, 845 cmÀ1
;
HR-MS: m/z=510.3402, calcd. for C36H47P: 510.3415; anal.
calcd. for C36H47P (510.73): C 84.66, H 9.28; found: C 84.51,
H 9.20.
Di-4-diamantylphosphine oxide (11)
(150 MHz, CDCl3): d=45.8 (C-2,12), 45.6 [d, 1J
A
5
Compound 9 (1 g, 2.19 mmol) was refluxed in toluene
(40 mL) for 24 h under argon with HSiCl3 (1.5 mL,
14.8 mmol). The solution was cooled to room temperature
and quenched with toluene (50 mL) and 20% NaOH solu-
tion (100 mL). The phases were separated and aqueous
phase was extracted with toluene (40 mL). Combined organ-
ic extracts were washed with distilled water (80 mL) and
stirred for 1 h with 30% H2O2 (15 mL). The reaction mix-
ture was diluted with distilled water (60 mL) and CH2Cl2
(80 mL). After phase separation the aqueous phase was ex-
tracted with CH2Cl2 (60 mL) and the combined organic ex-
tracts were washed with distilled water (60 mL) and dried
over Na2SO4. Purification was achieved by column chroma-
tography on silica gel (CH2Cl2:MeOH 95:5, Rf: 0.44); yield:
921 mg (2.18 mmol, 99%); mp 3208C (decomposition);
1H NMR (400 MHz, CDCl3): d=5.78 (d, J=424.9 Hz, 1H,
P-H), 2.04–1.90 (m, 12H, H-3,5,13), 1.87 (br s, 6H, H-
2,6,12), 1.83–1.69 (m, 20H, H-1,7,8,9,10,11,14); 13C NMR
(100 MHz, CDCl3): d=37.7 (C-8,10,14), 37.6 (C-3,5,13), 36.7
58.9 Hz, C-9], 44.9 (C-16), 44.4 [d, J
A
37.9–37.75 (m,
(m,
C-14,17,18),
37.68–37.48
C-
3,7,8,10,11,13), 34.7 (C-4), 34.1 (C-6), 33.6 [d, 3J(13C,31P)=
ACHTUNGTERNNUNG
10.6 Hz, C-1], 27.7 (C-15); 31P NMR (162 MHz, CDCl3,
H3PO4 external standard): d=86.33; IR (KBr): n=2909,
2869, 1445, 1336, 1306, 1223, 1057, 1001, 846, 755, 601,
546 cmÀ1; HR-MS: m/z=560.3001, calcd. for C36H46ClOP:
560.2975. anal. calcd. for C36H46ClOP (561.18): C 77.05, H
8.26; found: C 77.01, H 8.30.
Di-9-diamantylphosphine (9)
Compound 7 (900 mg, 1.97 mmol) was refluxed in toluene
(40 mL) for 18 h under argon with HSiCl3 (0.9 mL,
8.9 mmol). The solution was cooled to room temperature
and toluene (50 mL) followed by 20% NaOH solution
(80 mL) were added. After phase separation the aqueous
phase was extracted with toluene (80 mL); combined ex-
tracts were washed with distilled water (60 mL) and dried
over Na2SO4. Purification was achieved by column chroma-
tography on silica gel (CH2Cl2, Rf: 0.68); yield: 676 mg
(1.66 mmol, 84%); mp 241–2528C; 1H NMR (400 MHz,
CDCl3): d=2.83 (d, J=208.9 Hz, 1H, P-H), 1.94–1.80 (m,
12H, H-3,5,13), 1.76 (br s, 8H, H-2,6,9,12), 1.73–1.66 (m,
18H, H-1,7,8,10,11,14); 13C NMR (100 MHz, CDCl3): d=
[d, 3J
AHCTUNGTRENNUNG
(13C,31P)=11.1 Hz, C-2,6,12], 36.6 (C-1,7,11), 35.7 [d, 1J-
ACHTUNGTRENNUNG
(13C,31P)=61.4 Hz, C-4]; 31P NMR (162 MHz, CDCl3, H3PO4
external standard): d=60.53; IR (KBr): n=2880, 2846, 2262,
1458, 1439, 1314, 1258, 1176, 1048, 975, 909, 864 cmÀ1; HR-
MS: m/z=422.2727, calcd. for C28H39PO: 422.2739; anal.
calcd. for C28H39PO (422.58): C 79.58, H 9.30; found: C
79.31, H 9.39.
2
3
44.3 [d, J
8.0 Hz, C-2,6,12], 37.9 (C-8,10,14), 36.7 (C-1,7,11), 31.7 [d,
1J(13C,31P)=14.1 Hz, C-4], 25.7 (C-9); 31P NMR (162 MHz,
ACHTUNGTRENNUNG ACHTUNGTRENNUGN
(13C,31P)=10.1 Hz, C-3,5,13], 38.0 [d, J(13C,31P)=
ACHTUNGTRENNUNG
Di-9-triamantyphosphine oxide (12)
CDCl3, H3PO4 external standard): d=13.37; IR (KBr): n=
Compound 10 (70 mg, 0.14 mmol) in toluene (4 mL) was
mixed with 30% H2O2 (3 mL) and stirred at room tempera-
ture. After 1 h the reaction mixture was diluted with dis-
tilled water (50 mL) and CH2Cl2 (50 mL). The phases were
separated and the aqueous phase was extracted with CH2Cl2
(2ꢃ50 mL). Combined organic extracts were washed with
distilled water (50 mL) and dried over Na2SO4. Column
chromatography on silica gel with CH2Cl2:MeOH 95:5 (Rf:
0.57) gave 12; yield: 61 mg (0.12 mmol, 85%); mp >3508C;
1H NMR (400 MHz, CDCl3): d=5.71 (d, J=424.5 Hz, 1H,
P-H), 2.04–1.84 (m, 10H, H-8,10,15), 1.81 (br s, 4H, H-7,11),
1.77–1.63 (m, 20H, H-3,4,5,6,13,14,18), 1.57–1.45 (m, 8H, H-
2,12,17), 1.34–1.29 (m, 4H, H-16); 13C NMR (100 MHz,
2899, 2882, 2845, 2267, 1453, 1435, 1312, 1246, 1047, 966,
850 cmÀ1
; HR-MS: m/z=406.2790, calcd. for C28H39P:
406.2789; anal. calcd. for C28H39P (406.58): C 82.71, H 9.67;
found: C 82.38, H 9.93.
Di-9-triamantylphosphine (10)
Compound 8 (215 mg, 0.38 mmol) was refluxed in toluene
(15 mL) for 16 h under argon with HSiCl3 (0.3 mL, 3 mmol).
The solution was cooled to room temperature and CHCl3
(50 mL) followed by 20% NaOH solution (100 mL) were
added. After phase separation the aqueous phase was ex-
tracted with CHCl3 (2ꢃ50 mL); combined extracts were
Adv. Synth. Catal. 2010, 352, 609 – 615
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
613