1250
MUSLIN et al.
and extracted with benzene. The extract was dried
Scheme 4.
with Na2SO4, and the solvent was removed to obtain
15.5 g (88%) of phenol VI, mp 70 71 C [1].
C6H14, CCl4
Ia
IIa
Oxidation of phenol VI. Phenol VI, 1 g, in 50 ml
of a solvent (hexane or CCl4) was treated under argon
with 10.0 g of K3Fe(CN)6 in 50 ml of 2 M aqueous
KOH. After the initially appreared blue color had
disappered, the organic layer was separated, washed
with water, dried, and the solvent was removed in a
vacuum to obtain 0.95 g (95%) of biaryl IIa, mp 134
136 C [1].
IIIa
n-C6H14
,
n-C6H14
CCl4
CCl4
V
VII
OSiMe3
Cl
t-Bu
2,2 -Bis(trimethylsiloxy)-3,3 ,5,5 -tetra-tert-
butylbiphenylmercury (V) was obtained according
to [6] from 2.8 g of C6H5HgOH and 3.0 g of phenol
VI. Yield 1.5 g (38%), mp 145 150 C.
Bu-t
X
spectrophotometer for thin films or suspensions in
Vaseline oil.
Photolysis of biarylmercury V. a. Biarylmercury
V (3.0 g in 50 ml of hexane) decomposed after 10-h
irradiation with separation of 0.65 g (83.5%) of me-
tallic mercury. We obtained 1.2 g (56%) of [2,4-di-
tert-butyl)phenoxy]trimethylsilane (VI), mp 32 33 C
(from ethanol) [6].
Photolysis was performed in sealed ampules under
irradiation with a DRT-220 lamp.
4,6-Di-tert-butyl-2-chlorophenol (XI). Freshly
distilled sulfuryl chloride, 26 ml, was added with stir-
ring to 67.0 g of 2,4-di-tert-butylphenol in 150 ml of
diethyl ether. The reaction mixture was stirred for 1 h
at 20 C, washed with water and saturated with
b. Biarylmercury (V) (0.45 g in 7 ml CCl4) was
irradiated for 10 h. The postreaction mixture was
analyzed by GLC and HPLC and then treated with a
NaHCO3, and the organic layer was dried with an- saturated solution of sodium methoxide in methanol
hydrous Na2SO4. The solvent was removed, and the
residue was fractionated in a vacuum to obtain 55.0 g
(70%) of compound XI, bp 105 106 C (1 mm) [9].
according to [11].
REFERENCES
(4,6-Di-tert-butyl-2-chlorophenoxy)trimethyl-
silane (X). A solution of 2.4 g of chlorophenol XI,
2.0 ml of Me3SiCl, and 3.0 ml of Et3N in 50 ml of
anhydrous benzene was heated under reflux with stir-
ring under argon for 5 h. After cooling and filtering,
the solvent was removed under reduced pressure to
obtain 2.9 g (92%) of compound X, mp 89 90 C
1. Razuvaev, G.A., Vasileiskaj, N.S., and Muslin, D.V.,
J. Organomet. Chem., 1967, vol. 7, no. 3, pp. 531
533.
2. Razuvaev, G.A., Vasileiskaya, N.S., and Muslin, D.V.,
Dokl. Akad. Nauk SSSR, 1967, vol. 177, no. 3,
pp. 600 603.
1
3. Razuvaev, G.A., Muslin, D.V., Klimov, E.S., Lyapi-
na, N.Sh., and Vasileiskaya, N.S., Dokl. Akad. Nauk
SSSR, 1976, vol. 231, no. 4, pp. 897 899.
(from ethanol). IR spectrum, , cm : 1245, 835
(Me3Si); 930 (Si OAr). Found, %: C 65.43; N 9.335;
Si 9.54. C17N29ClOSi. Calculated, %: C 65.24; H 9.35;
Si 8.97.
4. Muslin, D.V., Lyapina, N.Sh., Klimov, E.S., Kirili-
cheva, V.G., and Razuvaev, G.A., Izv. Akad. Nauk
SSSR, Ser. Khim., 1980, no. 6, pp. 1385 1389.
(2,4-Di-tert-butylphenoxy)trimethylsilane (VII)
was obtained similarly to phenoxysilane X, mp 32
33 C (from ethanol) [10].
5. Ingold, C.K. and Roberts, B.P., Free-Radical Substi-
tution Reactions, New York: Interscience, 1971.
Translated under the title Reaktsii svobodnoradikal’-
nogo zameshcheniya, Moscow: Mir, 1974, p. 106.
4,6-Di-tert-butyl-2-(trimethylsilyl)phenol (VI).
A solution of 20.0 g of 2-bromo-(4,6-di-tert-butyl-
phenoxy)trimethylsilane [1] in diethyl ether was added
dropwise with stirring under argon to 2.1 g of finely
cut lithium in 50 ml of freshly distilled diethyl ether.
After the reaction had began, the reaction mixture was
stirred for 1 h and then cooled, the organic layer was
separated, hydrolyzed with saturated aqueous NH4Cl,
6. Razuvaev, G.A., Vasileiskaya, N.S., and Vavili-
na, N.N., Zh. Obshch. Khim., 1974, vol. 44, no. 1,
pp. 135 142.
7. Makarov, L.G. and Nesmeyanov, A.N., Metody
elementoorganicheskoi khimii. Rtut’ (Methods of
Organoelement Chemistry. Mercury), Nesmeya-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001
Muslin
