Phosphaalkynes
4558±4566
4J"H,P) 2.2 Hz, 9H, C"CH3)3], 1.63 [dd, 4J"H,P) 1.8, 0.7 Hz, 9H,
C"CH3)3], 4.69 [dsept, 3J"H,H) 6.6 Hz, 3J"H,P) 2.7 Hz, 1H, CH"CH3)2];
13C NMR "C6D6, 50.3 Hz, 258C): d 27.6 [d, 3J"C,P) 12.1 Hz, CH"CH3)2],
32.0 [d, 3J"C,P) 13.4 Hz, C"CH3)3], 35.4 [dd, 3J"C,P) 11.0, 8.6 Hz,
C"CH3)3], 37.4 [dd, 2J"C,P) 21.8, 17.3 Hz, C"CH3)3], 38.2 [dd, 2J"C,P)
19.1, 3J"C,P) 2.5 Hz, C"CH3)3], 53.2 [dd, 2J"C,P) 17.1 Hz, 3J"C,P)
2.5 Hz, CH"CH3)2], 193.8 [dd, 1J"C,P) 59.8 Hz, 2J"C,P) 3.7 Hz,
CC"CH3)3], 202.2 [dd, 1J"C,P) 62.3, 52.5 Hz, CC"CH3)3]; 31P NMR
"C6D6, 81.0 MHz, 258C): d 148.1, 247.3 [each d, 2J"P,P) 34.9 Hz]; MS
0.7 Hz, C"CH3)3], 211.8 [X part of A2BX spin system, jJ"P,P) j 8.0 Hz,
1J"C,P) 77.0 Hz, 3J"C,P) 15.2 Hz, "nA À nB) 10.2 Hz, ring C]; 31P NMR
"C6D6, 81.0 MHz, 258C): d 232.6 "s); MS "70 eV, EI): m/z "%): 300 "39)
[M] , 169 "100) [M À C5H9P2] , 100 "32) [M À C10H18P2] ; C15H27P3 "300.30).
2,4,6-Trisꢀ1-adamantyl)-1,3,5-triphosphabenzene ꢀ8b): Compound 9a
"140 mg, 0.60 mmol) in toluene "3 mL) and 1b "428 mg, 2.4 mmol) in
toluene "3 mL) produced 8b "150 mg, 36%) as a yellowpowder. 1H NMR
"C7D8, 400 MHz, 258C): d 1.75 [m, 18H, CH2], 2.13 [m, 9H, CH], 2.48 [m,
18H, CH2]; 13C NMR "CD2Cl2, 100.6 MHz, 258C): d 30.4 [s, CH], 37.0 [s,
CH2], 38.7 [X part of A2BX spin system, jJ"P,P) j 5.9 Hz, 3J"C,P)
15.5 Hz, 5J"C,P) 1.0 Hz, "nA À nB) 0.1 Hz, CH2], 46.5 [X part of A2BX
"70 eV, EI): m/z "%): 257 "29) [M] , 242 "6) [M À CH3] , 200 "12) [M À
C3H7N] , 84 "100) [C4H5P] ; elemental analysis calcd for C13H25NP2
"257.30): C 60.69, H 9.76, N 5.44; found C 59.7, H 9.8, N 5.1.
spin system, jJ"P,P) j 6.0 Hz, 2J"C,P) 22.0 Hz, 4J"C,P) 1.5 Hz, "nA
À
nB) 0.8 Hz, adamantyl-C], 212.2 [X part of A2BX spin system, jJ"P,P) j
5.9 Hz, 1J"C,P) 77.5 Hz, 3J"C,P) 15.5 Hz, "nA À nB) 10.2 Hz, ring-C];
31P NMR "C6D6, 81.0 MHz, 258C): d 238.1 "s); MS "70 eV, EI): m/z "%):
3,5-Di-tert-butyl-1-n-propyl-1,2,4-azadiphosphole ꢀ13b): Compound 9 f
"118 mg, 0.28 mmol) and 1a "28 mg, 0.28 mmol) furnished 13b "39 mg,
55%) as a colorless oil "b.p. 1408C at 10À2 mbar); 1H NMR "C6D6,
200 MHz, 258C): d 0.81 [t, 3J"H,H) 6.8 Hz, 3H, CH2CH2CH3], 1.36 [d,
4J"H,P) 1.6 Hz, 9H, C"CH3)3], 1.46 [ps, 3J"H,H) 6.8 Hz, 2H,
CH2CH2CH3], 1.62 [d, 4J"H,P) 1.8 Hz, 9H, C"CH3)3], 4.10 [m, 2H,
CH2CH2CH3]; 13C NMR "C6D6, 50.3 Hz, 258C): d 11.35 [s, CH2CH2CH3],
19.39 [d, 3J"C,P) 2.78 Hz, CH2CH2CH3], 33.7 [d, 3J"C,P) 15.8 Hz,
C"CH3)3], 35.7 [dd, 3J"C,P) 12.1, 9.2 Hz, C"CH3)3], 37.6 [dd, 2J"C,P)
33.8, 21.6 Hz, C"CH3)3], 38.7 [dd, 2J"C,P) 21.4 Hz, 3J"C,P) 3.0 Hz,
C"CH3)3], 53.1 [dd, 2J"C,P) 15.4 Hz, 3J"C,P) 3.0 Hz, CH2CH2CH3],
198.6 [dd, 1J"C,P) 45.4 Hz, 2J"C,P) 7.3 Hz, CC"CH3)3], 203.8 [dd,
1J"C,P) 45.1, 38.7 Hz, CC"CH3)3]; 31P NMR "C6D6, 81.0 MHz, 258C):
534 "21) [M] , 325 "100) [M À C11H15P2] ; C33H45 P3 "534.64).
2,4,6-Trisꢀ1,1-dimethylpropyl)-1,3,5-triphosphabenzene ꢀ8c): Compound
9a "305 mg, 1.34 mmol) in toluene "3 mL) and 1c "612 mg, 5.36 mmol)
produced 8c "271 mg, 59%) as an orange-yellowoil. 1H NMR "CDCl3,
200 MHz, 258C): d 0.84 [t, 3J"H,H) 7.4 Hz, 9H, CH2CH3], 1.74 [s, 18H,
C"CH3)2C2H5], 2.14 [q, 3J"H,H) 7.4 Hz, 6H, CH2CH3]; 13C NMR "CDCl3,
50.3 MHz, 258C): d 9.2 [s, CH2CH3], 32.7 [m, C"CH3)C2H5], 40.5 [m,
CH2CH3], 46.9 [m, C"CH3)C2H5], 208.8 [m, ring C][25]
;
31P NMR "CDCl3,
81.0 MHz, 258C): d 238.8 "s); MS "70 eV, EI): m/z "%): 342 "31) [M] , 197
"100) [M À C6H11P2] , 114 "9) [C6H11P] ; elemental analysis calcd for
2
d 154.1, 259.3 [each d, J"P,P) 29.7 Hz]; MS "70 eV, EI): m/z "%): 257
C18H33P3 "342.38): C 63.15, H 9.71; found C 63.13, H 10.1.
"100) [M] , 242 "4) [M À CH3] , 214 "5) [M À C3H7] ; C13H25NP2 "257.30).
2,4,6-Trisꢀ1-methylcyclopentyl)-1,3,5-triphosphabenzene ꢀ8d): Compound
9a "313 mg, 1.37 mmol) in toluene "3 mL) and 1d "691 mg, 5.48 mmol)
3,5-Di-tert-butyl-1-ꢀ2,2-dimethyl)propyl-1,2,4-azadiphosphole ꢀ13c): Com-
pound 9g "157 mg, 0.65 mmol) and 1a "65 mg, 0.65 mmol) furnished 13c
"80 mg, 87%) as a white powder "b.p. 1508C at 10À2 mbar); 1H NMR
produced 8d "192 mg, 37%) as a yellowpowder.
1H NMR "CDCl3,
200 MHz, 258C): d 1.54 [s, 9H, CH3], 1.78 ± 1.94 [m, 12H, CH2], 2.24 ±
2.42 [m, 12H, CH2]; 13C NMR "CDCl3, 100.6 MHz, 258C): d 22.9 [s,
cyclopentyl-CH2], 35.4 [m, CH3], 42.3 [m, cyclopentyl-CH2], 55.6 [m,
4
"C6D6, 200 MHz, 258C): d 0.96 [s, 9H, CH2C"CH3)3], 1.45 [d, J"H,P)
1.7 Hz, 9H, C"CH3)3], 1.64 [d, 4J"H,P) 1.5 Hz, 9H, C"CH3)3], 4.13 [dd,
3J"H,P) 14.4, 4J"H,P) 0.7, 2H, CH2C"CH3)3]; 13C NMR "C6D6, 50.3 Hz,
258C): d 28.8 [s, CH2C"CH3)3], 30.25 [d, 3J"C,P) 2.4 Hz, CH2C"CH3)3],
33.1 [d, 3J"C,P) 14.9 Hz, C"CH3)3], 35.4 [dd, 3J"C,P) 11.7, 8.6 Hz,
C"CH3)3], 37.1 [dd, 2J"C,P) 34.8, 21.1 Hz, C"CH3)3], 38.5 [dd, 2J"C,P)
C"CH2)2CH3], 211.8 [m, ring C][25]
;
31P NMR "CDCl3, 81.0 MHz, 258C):
d 234.2 "s); MS "70 eV, EI): m/z "%): 378 "33) [M] , 221 "100) [M À
C7H11P2] , 126 "15) [C7H11P] ; elemental analysis calcd for C21H33 P3
"378.42): C 66.65, H 8.79; found C 66.5, H 9.0.
3
2
3
19.6 Hz, J"C,P) 3.9 Hz, C"CH3)3], 61.9 [dd, J"C,P) 16.4 Hz, J"C,P)
3.1 Hz, CH2C"CH3)3], 195.6 [dd, 1J"C,P) 55.6 Hz, 2J"C,P) 4.5 Hz,
CC"CH3)3], 202.0 [dd, 1J"C,P) 56.3, 36.0 Hz, CC"CH3)3]; 31P NMR
"C6D6, 81.0 MHz, 258C): d 148.6, 258.8 [each d, 2J"P,P) 26.2 Hz]; MS
2,4,6-Trisꢀ1-methylcyclohexyl)-1,3,5-triphosphabenzene ꢀ8e): Compound
9a "209 mg, 0.92 mmol) in toluene "2 mL) and 1e "516 mg, 3.68 mmol)
produced 8e "170 mg, 44%) as a yellowpowder. 1H NMR "C6D6, 200 MHz,
258C): d 1.36 ± 1.74 [m, 18H, CH2], 1.65 [s, 9H, CH3], 2.05 ± 2.11 [m, 6H,
CH2], 2.81 ± 2.88 [m, 6H, CH2]; 13C NMR "C6D6, 100.6 MHz, 258C): d
23.2 [s, cyclohexyl-CH2], 26.6 [s, cyclohexyl-CH2], 35.8 [m, CH3], 41.6
[pseudo t, 3J"C,P) 16.2 Hz, cyclohexyl-CH2], 47.6 [pseudo-t, 2J"C,P)
"70 eV, EI): m/z "%): 285 "100) [M] , 270 "20) [M À CH3] , 228 "5) [M À
C5H11N] ; C15H29NP2 "285.35).
3,5-Di-tert-butyl-1-cyclohexyl-1,2,4-azadiphosphole ꢀ13d): Compound 9h
"199 mg, 0.78 mmol) and 1a "78 mg, 0.78 mmol) furnished 13d "71 mg,
61%) as a colorless oil "b.p. 1808C at 10À2 mbar); 1H NMR "C6D6,
200 MHz, 258C): d 0.76 ± 2.15 [m, 28H, C"CH3), cyclohexyl-CH2], 4.33 [s,
1H, NCH]; 13C NMR "C6D6, 50.3 Hz, 258C): d 22.7 [s, CH2], 23.55 [s,
CH2], 27.30 [d, 3J"C,P) 4.5 Hz, CH2], 33.9 [d, 3J"C,P) 14.5 Hz, C"CH3)3],
35.0 [dd, 3J"C,P) 10.39, 7.5 Hz, C"CH3)3], 37.1 [dd, 2J"C,P) 30.1, 18.0 Hz,
C"CH3)3], 38.7 [dd, 2J"C,P) 20.0 Hz, 3J"C,P) 4.0 Hz, C"CH3)3], 56.9 [dd,
2J"C,P) 20.54, 3J"C,P) 5.4 Hz, NCH], 197.6 [dd, 1J"C,P) 50.0 Hz,
2J"C,P) 5.2 Hz, CC"CH3)3], 202.5 [dd, 1J"C,P) 43.2, 39.7 Hz, CC"CH3)3];
31P NMR "C6D6, 81.0 MHz, 258C): d 147.1, 250.0 [each d, 2J"P,P)
19.5 Hz, C"CH2)2CH3], 212.1 [m, ring C][25]
;
31P NMR "C6D6, 81.0 MHz,
258C): d 242.8 "s); MS "70 eV, EI): m/z "%): 420 "18) [M] , 249 "100)
[M À C8H13P2] , 140 "7) [C8H13P] ; C24H39P3 "420.50).
2,4-Bisꢀ1-adamantyl)-6-tert-butyl-1,3,5-triphosphabenzene ꢀ21): Com-
pound 1a "59 mg, 0.59 mmol) was added at À788C to a solution of 9a
"140 mg, 0.59 mmol) in toluene "5 mL) and the mixture was then allowed to
warm to room temperature. After cooling back to À788C a solution of 1b
"320 mg, 1.77 mmol) in toluene "2 mL) was added and the mixture was
allowed to warm up. The solvent was distilled off under reduced pressure
"208C at 10À2 mbar). The residue was redissolved in n-pentane and purified
by column chromatography on silica gel "deactivated with 4% water,
column: 20 Â 2.0 cm). The yellowfraction "210 mg) was found to contain 21
contaminated by traces of 8b. 31P NMR "C6D6, 81.0 MHz, 258C): d 237.0,
237.2 [AB2 spin system, 2J"P,P) 6.2 Hz]; MS "70 eV, EI): m/z "%): 456 "5)
27.13 Hz]; MS "70 eV, EI): m/z "%): 297 "100) [M] , 214 "17) [M À
C6H11] , 200 "2) [M À C6H11N] ; C16H29NP2 "297.36).
General procedure for the preparation of the 1,3,5-triphosphabenzenes
8a ± e: Four equivalents 1 a ± e were added at À788C to a solution of 9a in
toluene. After the mixture was allowed to warm up, toluene was distilled
off at 208C at 10À2 mbar, the residue was redissolved in n-pentane, and
purified by column chromatography on silica gel "deactivated with 4%
water, column: 20 Â 2.0 cm). The yellowfraction afforded 8a ± e after
removal of the solvent. In the cases of 8a ± c no further purification was
necessary, 8d and 8e were recrystallized from n-pentane.
[M] , 325 "100) [M À C5H9P2] ; C27H39P3 "456.53).[26]
6-ꢀ1-Adamantyl)-2,4-di-tert-butyl-1,3,5-triphosphabenzene ꢀ22): A solu-
tion of 1b "120 mg, 0.66 mmol) in toluene "3 mL) was added at À788C to
a solution of 9a "150 mg, 0.66 mmol) in toluene "5 mL), and the mixture
was then allowed to warm to room temperature. After cooling back to
À788C 1a "200 mg, 2.00 mmol) was added and the mixture allowed to
warm up again. The solvent was distilled off under reduced pressure "208C
at 10À2 mbar). The residue was redissolved in n-pentane and purified by
column chromatography on silica gel "deactivated with 4% water, column:
2,4,6-Tri-tert-butyl-1,3,5-triphosphabenzene ꢀ8a): Compound 9a "100 mg,
0.47 mmol) in toluene "5 mL) and 1a "180 mg, 1.8 mmol) produced 8a
"120 mg, 68%) as a yellowpowder. 1H NMR "[D8]THF, 400 MHz, 258C):
d 1.34 [s, 27H, C"CH3)3]; 13C NMR "[D8]THF, 100.6 MHz, 258C): d
36.1 [X part of A2BX spin system, jJ"P,P) j 8.0 Hz, 3J"C,P) 14.5 Hz,
5J"C,P) 1.1 Hz, "nA À nB) 0.1 Hz, C"CH3)3], 44.53 [X part of A2BX spin
system, jJ"P,P) j 8.1 Hz, 2J"C,P) 24.5 Hz, 4J"C,P) 1.6 Hz, "nA À nB)
20 Â 2.0 cm). The yellowfraction "200 mg) was found to contain
22
contaminated by traces of 8a. 31P NMR "C6D6, 81.0 MHz, 258C): d 235.2,
235.4 [AB2 spin system, 2J"P,P) 7.9 Hz]; MS "70 eV, EI): m/z "%): 378 "14)
[M] , 169 "100) [M À C11H15P2] ; C21H33P3 "378.42).[26]
Chem. Eur. J. 2000, 6, No. 24
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
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4565