2
838
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 12, December, 2015
Moskalev et al.
Chemical shifts are given in ppm, using chemical shifts of proꢀ
tons and carbon atoms of deuterated solvents as references. EPR
spectra were recorded on a Bruker ER 200 DꢀSRC spectrometer
dissolved in diethyl ether (10 mL). Compound 5 (0.077 g, 18%)
was isolated by concentration of the solution, yellow plate crysꢀ
tals, m.p. 156—158 °C. Found (%): C, 88.96; H, 7.31. C H N
3
2
31
–
1
(
9.46 MHz). Melting points were determined in sealed evacuatꢀ
(429.58 g mol ). Calculated (%): C; 89.39; H, 7.22. IR (Nujol),
–
1
ed capillary tubes.
Catalytic reactions were carried out in sealed NMR tubes.
The samples were prepared as follows.
ν/cm : 1646 s, 1614 s, 1585 s, 1542 w, 1487 w, 1432 m, 1363 m,
1325 m, 1264 m, 1254 w, 1245 w, 1228 w, 1209 w, 1196 w, 1180 m,
1161 w, 1106 m, 1097 m, 1073 w, 1059 w, 1036 m, 1009 w,
935 w, 925 w, 914 m, 897 w, 847 w, 831 s, 782 s, 763 s, 749 w, 702 s,
A. In the case of hydroamination of alkynes 2a—g with
1
4
0
ꢀchloroaniline, an alkyne (0.89 mmol), 4ꢀchloroaniline (0.113 g,
.89 mmol), and compound 1 (0.022 g, 0.0178 mmol) were placed
610 w, 600 w, 544 w, 534 w. H NMR (400 MHz, C D , 298 K),
6
6
δ: 7.36—7.12 (m, 10 H, CHarom); 6.94 (dd, 1 H, CHarom, J = 8.0 Hz,
J = 7.8 Hz); 6.90—6.84 (m, 2 H, CHarom); 6.46 (d, 1 H, CHarom
J = 7.3 Hz); 3.28 (sept, 2 H, —CH(CH ) , J = 6.9 Hz); 3.19 (s, 3 H,
into an NMR tube. Then, deuterobenzene (0.65 mL) was vacuꢀ
um condensed into the tube, which was sealed and placed in
a thermostat with the temperature of 90 °C.
,
3
2
=C(CH )(Ph)); 1.28 (d, 6 H, —CH(CH ) , J = 6.8 Hz); 1.03
3
3 2
B. To study the influence of the concentration of substrates
and the concentration of complex 1 on the rate of hydroaminaꢀ
tion, phenylacetylene (0.23—1.43 mmol), 4ꢀchloroaniline
(d, 6 H, —CH(CH ) , J = 7.0 Hz).
3
2
{Nꢀ(2,6ꢀDiisopropylphenyl)ꢀ2ꢀ(1ꢀphenylvinyl)acenaphthylꢀ
eneꢀ1(2H)ꢀimineꢀ2ꢀ[(E)ꢀ2ꢀphenylethꢀ1ꢀenyl]gallium} bisꢀphenylꢀ
(
0.13—1.37 mmol), and compound 1 ((0.88—4.32)•10–2 mmol),
acetylide, [C12H (NC H Pr )(PhC=CH )(PhC=CH)]Gaꢀ
i
6
6
3
2
2
depending on the required ratio of components, were placed
into an NMR tube. Then, deuterobenzene was vacuum conꢀ
densed into the tube to a total volume of the reaction mixture of
(C≡CPh) (6). Phenylacetylene (2b) (0.51 g, 5 mmol) was added
2
to complex 1 (0.57 g, 0.5 mmol) obtained in situ from dppꢀbian
(0.5 g, 1 mmol) in toluene (30 mL). The solution immediately
changed the color from dark blue to reddish brown. The reaction
mixture was heated at 120 °C for 15 h. Then, toluene was evapoꢀ
rated in vacuo, whereas anhydrous residue was dissolved in diꢀ
ethyl ether (15 mL). After 2 h, a fine crystalline yellow precipiꢀ
tate was formed and filtered off. The solution left after the sepaꢀ
ration of the fine crystalline yellow precipitate of acenaphthenenꢀ
imine 5 was concentrated to 5 mL, complex 6 (0.10 g, 13%) was
isolated by crystallization from this solution as light yellow
needleꢀlike crystals, m.p. 176—178 °C (decomp.). Found (%):
0
.65 mL. The tube was sealed and placed in a thermostat with
the temperature of 90 °C.
C. In the case of comparative test of the catalytic activity of
complexes 6, 7, 9, and 10, phenylacetylene (2b) (0.091 g,
0
.89 mmol), 4ꢀchloroaniline (0.113 g, 0.89 mmol), and a cataꢀ
lyst in the amount corresponding to the molar percents indicated
in Table 3 relative to the amount of one of the substrates were
placed into an NMR tube. Then, deuterobenzene (0.65 mL) was
vacuum condensed into the tube, which was sealed and placed in
a thermostat with the temperature of 90 °C.
–
1
C, 84.21; H, 5.97. C H GaN (802.66 g mol ). Calculated (%):
56
46
1
–1
In all the cases, the processes were monitored by H NMR
C, 83.72; H, 5.73. IR (Nujol), ν/cm : 2139 m, 1950 w, 1811 w,
1673 w, 1630 s, 1620 m, 1953 s, 1537 w, 1486 m, 1344 m, 1324 m,
1264 m, 1246 w, 1211 s, 1188 m, 1157 w, 1102 m, 1069 m, 1057 m,
1028 s, 998 w, 954 m, 927 m, 913 s, 898 m, 878 w, 858 w, 836 s,
822 w, 807 m, 786 s, 774 w, 760 s, 751 s, 716 m, 702 m, 691 s,
632 w, 598 m, 563 s, 549 w, 535 s, 523 w, 507 w, 496 w, 474 w.
spectroscopy, recording spectra through a certain period of time,
cooling the sample to room temperature. The ratio between the
starting reagents and the reaction products was calculated from
the integral intensities of the corresponding signals.
Nꢀ(4ꢀChlorophenyl)hexaneꢀ2ꢀimine, 4ꢀClC H N=C(Me)ꢀ
6
4
1
1
(
CH ) Me (3a). H NMR (400 MHz, C D , 298 K), δ: 7.09 (d, 2 H,
H NMR (200 MHz, tolueneꢀd , 293 K), δ: 7.95 (d, 2 H, CHarom,
2
3
6
6
8
CHarom, J = 8.8 Hz); 6.40 (d, 2 H, CHarom, J = 8.5 Hz); 2.12 (t, 2 H,
N=C(Me)CH CH CH Me, J = 7.5 Hz); 1.57—1.47 (m, 2 H,
J = 7.1 Hz); 7.54 (dd, 2 H, CHarom, J = 7.8 Hz); 7.40—7.21 (m,
9 H, CHarom); 7.20—7.09 (m, 3 H, CHarom); 7.08—6.96 (m, 5 H,
CHarom); 6.95—6.88 (m, 3 H, CHarom); 6.81—6.73 (m, 3 H,
2
2
2
N=C(Me)CH CH CH Me); 1.36 (s, 3 H, N=C(Me)CH CH ꢀ
2
2
2
2
2
CH Me); 1.32—1.21 (m, 2 H, N=C(Me)CH CH CH Me); 0.87
CHarom); 6.63 (t, 1 H, CHarom, J = 7.8 Hz); 6.30 (d, 2 H, CHarom,
2
2
2
2
(
t, 3 H, N=C(Me)CH CH CH Me, J = 7.4 Hz).
J = 7.3 Hz); 6.25 (s, 1 H, HC=C(Ph)); 5.42 (s, 1 H, HC=C(Ph));
2
2
2
Nꢀ(4ꢀChlorophenyl)ꢀ1ꢀphenylethaneꢀ1ꢀimine, 4ꢀClC H ꢀ
3.99 (sept, 1 H, CH(CH ) , J = 6.7 Hz); 2.76 (sept, 1 H,
6
4
3 2
1
N=C(CH )Ph (3b). H NMR (400 MHz, C D , 298 K), δ:
CH(CH ) , J = 6.7 Hz); 1.73 (d, 3 H, CH(CH ) , J = 6.7 Hz);
3
6
6
3 2
3 2
7
.95—7.85 (m, 2 H, CHarom); 7.21—7.16 (m, 3 H, CHarom); 7.10
1.27 (d, 3 H, CH(CH ) , J = 6.7 Hz); 1.11 (d, 3 H, CH(CH ) ,
3 2 3 2
(
1
d, 2 H, CHarom, J = 7.8 Hz); 6.45 (d, 2 H, CHarom, J = 7.8 Hz);
J = 7.0 Hz); 0.13 (d, 3 H, CH(CH ) , J = 6.8 Hz).
3 2
1
2
.76 (s, 3 H, N=C(CH )Ph).
Gallium [N ,N ꢀbis(2,6ꢀdiisopropylphenyl)acenaphthyleneꢀ
1,2ꢀdiamide] bisꢀphenylamide, (dppꢀbian)Ga[N(H)Ph]2 (7).
Phenylacetylene (2b) (0.1 g, 1 mmol) and aniline (0.09 g, 1 mmol)
were added to complex 1 (0.57 g, 0.5 mmol) obtained in situ
from dppꢀbian (0.5 g, 1 mmol) in benzene (30 mL). The reaction
mixture changed the color from dark blue to reddish brown.
Then, the mixture was heated for 15 min at 90 °C and concenꢀ
trated by evaporation of the solvent in vacuo. After a while, dark
brown prismatic crystals of compound 7 (0.36 g, 40%) were isoꢀ
lated from the solution, m.p. 145 °C. Found (%): C, 79.64;
3
Nꢀ(4ꢀChlorophenyl)ꢀ1ꢀ(pꢀtolyl)ethaneꢀ1ꢀimine, 4ꢀClC H ꢀ
6
4
1
N=C(Me)(4ꢀMeC H ) (3c). H NMR (200 MHz, C D , 298 K),
δ: 7.88 (d, 2 H, CHarom, J = 8.0 Hz), 7.11 (d, 2 H, CHarom
J = 8.5 Hz); 7.03 (d, 2 H, CHarom, J = 7.8 Hz); 6.47 (d, 2 H,
CHarom, J = 8.3 Hz); 2.12 (s, 3 H); 1.79 (s, 3 H).
6
4
6
6
,
1
ꢀ[Nꢀ(2,6ꢀDiisopropylphenyl)imino]ꢀ2ꢀ(1ꢀphenylethylidene)ꢀ
i
acenaphthene, C12H (NC H Pr )(=C(Ph)CH ) (5). Phenylꢀ
6
6
3
2
3
acetylene (2b) (0.51 g, 5 mmol) to complex 1 (0.57 g, 0.5 mmol)
obtained in situ from dppꢀbian (0.5 g, 1 mmol) in toluene (30 mL).
The solution immediately changed the color from dark blue to
reddish brown. The reaction mixture was heated at 120 °C for 15 h.
Then, toluene was evaporated in vacuo, the dry residue was disꢀ
solved in diethyl ether (15 mL). After 2 h, a fine crystalline
yellow precipitate was formed, which was filtered and once more
–
1
H, 6.87. C H GaN •2C H (910.87 g mol ). Calculated (%):
4
8
52
4
6
6
C, 79.05; H, 7.06. IR (Nujol), ν/cm–1: 3396 w, 3376 m, 1941 w,
1667 w, 1596 s, 1580 w, 1495 s, 1441 m, 1426 w, 1364 m, 1321 m,
1292 s, 1255 m, 1215 w, 1179 m, 1149 m, 1110 m, 1077 m, 1057 m,
992 m, 951 w, 937 m, 892 m, 871 w, 853 s, 820 s, 808 s, 787 w,