PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
11
CH), 7.49 (1H, s, aryl CH), 4.70 [2H, hept, J(H-H) ¼ aggregate on the side of the flask. After cooling to room
6.0 Hz, OCH], 4.69 [2H, hept, J(H-H) ¼ 6.0 Hz, OCH], 2.65
temperature the material was filtered and the precipitate was
collected. The precipitate was combined with the aggregate
and dissolved in DMF:water (90:10 v/v) until completely
solubilized. The concentrate was allowed to sit sealed in a
(3H, s br, CH3), 1.37 [12H, d, J(H-H) ¼ 6.0 Hz, CH3], 1.25
[12H, dd, J(H-H) ¼ 6.5 Hz, J(H-H) ¼ 2.0 Hz, CH3]. 13C
NMR (acetone-d6): d 191.1 (s, C ¼ O), 154.5 (s, H3C-C ¼ C-
H), 144.5 (s, aryl C-C), 144.4 [d, J(P-H) ¼ 1.5 Hz, aryl C-C),
round bottom flask in the presence of sunlight. After a
144.0 (s, aryl C-C), 143.0 (s, aryl C-C), 141.4 (s, aryl C-C),
139.7 (s, aryl C-C), 133.1 [d, J(P-C) ¼ 6.2 Hz, aryl CH],
133.1 (d, J(P-C) ¼ 6.2 Hz, aryl CH), 129.8 (s, aryl CH),
128.2 (s, aryl CH), 128.2 (s, aryl CH), 128.1 (s, aryl CH),
127.9 [d, J(P-C) ¼ 3.7 Hz, aryl CH], 127.63 [d, J(P-C) ¼
3.7 Hz, aryl CH], 122.6 (s, vinyl CH), 71.1 [d, J(P-C) ¼
6.2 Hz, OCH], 71.0 [d, J(P-C) ¼ 6.2 Hz, OCH], 4.29 [d, J(P-
C) ¼ 1.2 Hz, CH3], 4.27 [d, J(P-C) ¼ 1.25 Hz, CH3], 4.14 [d,
J(P-C) ¼ 1.2 Hz, CH3], 4.10 [d, J(P-C) ¼ 1.2 Hz, CH3],
18.64 (s, CH3). 31P NMR (acetone-d6): d 17.0 (s), 16.8 (s).
Hexaisopropyl((1,3,5-triazine-2,4,6-triyl)tris(([1,10-
week, a beige crystal was observed. The crystal was deter-
mined to be co-crystallized with DMF. Yield 27.6%. 1H
NMR (methanol-d4): d 7.91 (4H, m, aryl CH), 7.83 (4H, m,
aryl CH), 4.90 (s, OH). 13C NMR (methanol-d4): d 144.6
[dd, J(C-P) ¼ 1.3 Hz, J(C-P) ¼ 1.25 Hz, aryl C), 132.7 [d,
J(C-P) ¼ 186 Hz, aryl C-P], 132.6 [d, J(C-P) ¼ 10 Hz, aryl
CH], 128.1 [d, J(C-P) ¼ 13 Hz, aryl CH]. 31P NMR (metha-
nol-d4): d 17.2 (s).
3,30,5,50-Tetra(phosphonic
acid)-1,10-biphenyl
(2c).
Prepared by an analogous route to compound 1c. The material
1
was dried but failed to crystallize. Yield > 99%. H NMR
biphenyl]-40-4-diyl)))tris(phosphonate) (7b). Prepared by
an analogous route to compound 1b. Yield: 3.71 g,
(methanol-d4): d 8.25 (6H, m, aryl CH), 5.46 (8H, s, OH). 13
C
NMR (methanol-d4): d 139.20 [t, J(P-C) ¼ 13 Hz, aryl C-C],
137.8 [d,d, J(P-C) ¼ 172 Hz, J(P-C) ¼ 12.5 Hz, aryl C-P], 131.3
[t, J(P-C) ¼ 131 Hz, aryl CH], 129.9 (m, aryl CH). 31P NMR
(methanol-d4): d 17.4 (s).
1
3.57 mmol, 69%. H NMR (acetone-d6): d 8.90 [6H, d, J(H-
H) ¼ 8.5 Hz, aryl CH], 7.96 [6H, dd, J(H-H) ¼ 8.0 Hz, J(H-
H) ¼ 12.5 Hz, aryl CH], 7.88 [6H, br d, J(H-H) ¼ 9.0 Hz,
aryl CH], 7.78 [6H, dd, J(H-H) ¼ 8.0 Hz, J(H-H) ¼ 3.5 Hz,
aryl CH], 4.74 (6H, m, OCH), 1.420 [18H, dd, J(P-H) ¼
28 Hz, J(H-H) ¼ 6.5 Hz, CH3], 1.28 [18H, dd, J(P-H) ¼
28 Hz, J(H-H) ¼ 6.5 Hz, CH3]. 13C NMR (acetone-d6): d
171.1 (s, aryl C-N), 143.8 (s, aryl C-C), 143.7 [d, J(P-C) ¼
3.75 Hz, aryl C-C], 135.6 (s, aryl C-C), 132.2 [d, J(P-C) ¼
10 Hz, aryl CH], 129.4 (s, aryl CH), 129.2 [d, J(P-C) ¼
190 Hz, aryl C-P], 127.3 (s, aryl CH), 126.9 [d, J(P-C) ¼
15 Hz, aryl CH], 70.7 [d, J(P-C) ¼ 5 Hz, OCH], 23.9 [d, J(P-
C) ¼ 5 Hz, CH3], 23.7 [d, J(P-C) ¼ 3.75 Hz, CH3]. 31P
NMR (acetone-d6): d 17.8.
1,3,5-Benzene-tri-p-phenylphosphonic acid (3c).[41]
Prepared by an analogous route to compound 1c. Yield
1
39.16%. H NMR (methanol-d4): d 7.92 (3H, m, aryl CH).
4.89 (6H, s, OH). 13C NMR (methanol-d4): d 137.1 (m, aryl
CH), 134.4 [dt, J(P-C) ¼ 12.5 Hz, J(P-C) ¼ 187.5 Hz, aryl
CH]. 31P NMR (methanol-d4): d 12.9 (s).
1,3,5-Tris(phenyl-4-phosphonic acid)benzene (BBTPA)
(4c). Prepared by an analogous route to compound 1c. Yield
1
74.28%. H NMR (methanol-d4): d 7.93 (6H, m, aryl CH),
7.860–7.88 (9H, m, aryl CH), 4.89 (6H, s, OH). 13C NMR
(methanol-d4): d 143.4 [s br, aryl C-C), 143.0 [d, J(P-C) ¼
2.5 Hz, aryl C-C), 132.5 [d, J(P-C) ¼ 10 Hz, aryl CH], 127.5
[d, J(P-C) ¼ 11.3 Hz, aryl CH], 125.9 (s, aryl CH). 31P NMR
(methanol-d4): d 17.4 (s).
1,3,5-tris(diisopropyl 2-methylphenyl-4-phosphonato)-
triazine (8b). Prepared by an analogous route to compound
1
1b. Yield: 5.24 g, 18.6 mmol, 73%. H NMR (acetone-d6): d
8.27 [3H, dd, J(H-H) ¼ 8.0 Hz, J(H-H) ¼ 4.5 Hz, aryl CH],
7.84 (6H, m, aryl CH), 4.76 [3H, hept, J(H-H) ¼ 6.0 Hz,
OCH), 4.74 [3H, hept, J(H-H) ¼ 6.0 Hz, OCH], 2.82 (9H, s,
aryl C-CH3), 1.42 [18H, d, J(H-H) ¼ 6.5 Hz, CH3], 1.28
[18H, d, J(H-H) ¼ 6.5 Hz, CH3]. 13C NMR (acetone-d6): d
173.1 [d, J(P-C) ¼ 1.25 Hz, aryl C-N], 138.7 [d, J(P-C) ¼
2.5 Hz, aryl C-C], 138.6 [d, J(P-C) ¼ 13.75 Hz, aryl CH],
134.4 [d, J(P-C) ¼ 10 Hz, aryl C-C], 133.2 [d, J(P-C) ¼
185 Hz, aryl C-P], 130.9 [d, J(P-C) ¼ 15 Hz, aryl CH], 128.7
[d, J(P-C) ¼ 10 Hz, aryl CH], 70.1 [d, J(P-C) ¼ 5 Hz, OCH],
23.1 [d, J(P-C) ¼ 3.75 Hz, CH3], 22.9 [d, J(P-C) ¼ 3.75 Hz,
CH3], 21.1 (s, CH3). 31P NMR (acetone-d6): d 16.1.
((1,3,5-phenyl-2,4,6-triyl)tris(([1,10-biphenyl]-40-4-diyl)))
tris(phosphonic acid) (5c). Prepared in an analogous route
1
to compound 1c. Yield: 26 mg, 26%. H NMR (methanol-
d4): d 7.89 (3H, s, aryl CH), 7.79 (24H, m, aryl CH). 31P
NMR (methanol-d4): d 17.0.
(E)-(40-(3-(40-phosphono-[1,10-biphenyl]-4-yl)but-2-enoyl)
-[1,10-biphenyl]-4-yl)phosphonic acid (6c). Prepared using a
modification of the previously reported method.[33] Compound
6b was dissolved in CH2Cl2 and added to a round bottom flask.
The flask was sealed and purged under an argon atmosphere.
Bromotrimethylsilane (2.0mL, 15mmol) was added portion-
wise via syringe and the reaction was allowed to stir at room
temperature for 12h. The resulting solution was unsealed and
concentrated by rotary evaporation. The crude product was
quenched by the addition of water, and NH4OH added to the
solution until the aggregate material in solution dissolved. The
solution was then extracted against CH2Cl2 (1ꢅ 100 mL). The
aqueous phase was collected and acidified. The aqueous phase
was allowed to sit until an aggregate appeared. The solution
Preparation of phosphonic acid derivatives
Biphenyl-4,40-di(phosphonic acid) (1c). Prepared using an
adaptation of the previously reported method.[41] To a
250 mL side-arm round bottom flask was added HCl
(100 mL) aqueous solution (6 M). A concentrated acetone
solution of 1b (10.0 g in 50 mL) was then added portion
wise to the water. The flask was then heated to reflux over-
was decanted and the aggregate dried to yield the title com-
1
night. After which a yellow solution was observed with dark pound. Yield: 0.494 g, 65%. H NMR (methanol-d4): d 8.13