Vol. 30, No. 4 (2018)
Synthesis of p-(Cyclohexene-3-yl-ethyl)phenol and Characteristics of its Phosphatization 765
TABLE-3
PHYSICO-CHEMICAL PROPERTIES OF TRI-[p-(CYCLOHEXENYL)PHENYL]PHOSPHITE
2
0
40
Structural formula
Empirical formula
Tboil. °C/5 mm Hz
nD
ρ4
m.w.
634
CH
O
P
C H O P
321-324
1.5715
1.0782
42
51
3
CH3
3
TABLE-4
COMPARATIVE TEST RESULTS OF TRI-[p-(CYCLOHEXENYL)PHENYL]PHOSPHITE
2
Viscosity (mm /sec, 100 °C)
Nominations
Sediment (%)
∆ν (%)
Pre-test
7.90
Post-test
8.75
Turbine oil T-46 (without addition of antioxidant)
T-46 + IKhP-21
2.17
0.90
0.15
10.76
7.18
3.80
8.63
9.25
T-46 + CAPh
8.56
8.37
and a glass tube for supplying of nitrogen to the system.
p-(Cyclohexenylethyl)phenol and toluene were added to the
flask in a calculated amount and heated.At 40 °C, phosphorus
trichloride was added dropwise using additional funnel.After
the addition of phosphorus trichloride, the reaction temperature
was raised to 50-80 ºC and the mixture was stirred for 2 to 5 h
again. The hydrogen chloride is removed from the reaction
through esterification in the presence of nitrogen gas atmos-
phere. Separated hydrogen chloride is trapped in an aqueous
solution of NaOH.
After the completion of esterification reaction, the reaction
mixture was transferred to Claisen flask and rectified, at first,
phosphorus trichloride and a solvent were distilled at atmos-
pheric pressure and then, unreacted p-(cyclohexenenylethyl)-
phenol and the target product tri-[p-(cyclohexenylethyl)phenyl]-
phosphite were distilled in the vacuum (at 10 mm Hg). For
the purpose of determining the optimal reaction conditions that
ensure the maximum yield of tri-[p-(cyclohexenylethyl)phenyl]-
phosphite, the temperature varied from 40 to 80 °C with constant
stirring from 1 to 5 h and the molar ratio of tri-[p-(cyclohexe-
nylethyl)]phenol to phosphorus trichloride (1:1::4:1) .
Analysis of the results obtained in the synthesis of tri-[p-
field of δ = 1.3 ppm, corresponding to methyl proton, multi-
plying signal in the field of δ = 1.35-1.70 ppm, corresponding
to the protons of cyclohexene ring and quadruplet A
2
B spin
2
system in the field of δ = 6.95 ppm, referring to the protons of
aromatic nuclear, but singlet in the field of 5-6 ppm, shifted
by dilution to strong field of (1H)–OH-group.
Synthesized tri-[p-(cyclohexenylethyl)phenyl]phosphite
was tested as an antioxidant of turbine oil T-46. The experi-
ments were carried out on DK-NAMI apparatus in comparison
to GOST 11063-77 at 100 °C in 30 h, in the amount of the
antioxidant of 0.5 % mass. The results of comparative tests
are shown in Table-4.
As seen from Table-4, addition of phosphite to the base
oil leads to improvement of its antioxidative properties. The
best efficiency is observed in the presence of phosphite, its
application allows accretion of oil viscosity (∆ν) at 100 °C
amounts to 3.8 %, but sediment amount, formed after oxidation
of 30 h-0.15 %; in the absence of base oil of antioxidant,
correspond to 10.76 and 2.17 %. Hence, the compound tri-[p-
cyclohexenylethyl)phenyl]phosphite can be recommended as
antioxidant for the turbine oil T-46.
Conclusion
(
cyclohexenylethyl)phenyl]phosphite makes possible to deter-
mine the optimum conditions for the phosphatization of p-
cyclohexenylethyl) phenol with phosphorus trichloride, which
are: temperature 70 °C, reaction time 4 h, the molar ratio of p-
cyclohexenylethyl)phenol to PCl , 3:1. Under these conditions,
Cycloalkenylation of phenol with 4-vinylcyclohexene was
carried out in the presence of zeolite-Y catalyst, saturated
by orthophosphoric acid on the batch unit. As a result, it was
found out that at optimum regime the yield of the target product
p-(cyclohexenylethyl)phenol amounts to 72.4 % of theory on
the phenol taken, but selectivity to 97.7 % on the target product.
Phosphatization of p-(cyclohexenylethyl)phenol with
phosphorus trichloride allows obtaining of tri[p-(cyclohexenyl)-
phenyl]phosphite with the yield of 88.6 % and its investigation
as an antioxidant for turbine oil T-46 resulted effectively.
(
(
3
the theoritical yield of the target product is 88.6 %. The
physico-chemical parameters of tri-[p-(cyclo-hexenyl)phenyl]-
phosphite are given in Table-3.
In IR spectra, the typical adsorption bands of tri-[p-
cyclohexenylethyl)phenyl]phosphate were identified as the
-1
bands at 1505 cm is due to skeleton vibrations of benzene
-1
ring and the bands at 825 cm refers to non-planar deformational
C-H vibrations of p-substituted aromatic nuclear. Adsorption
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-1
bands at 2920-2845 cm refers to valence vibrations of cyclo-
hexene ring and CH groups. Deformational vibrations of C-H
bond of CH -group are confirmed by the adsorption band in
the field of 1370 cm .Intensive adsorption bands in the field of
3
1
.
B.N. Gorbunov,Y.A. Gurvich and I.P. Maslova, Chemistry and Techno-
logy of Stabilizers of Polymeric Materials, Khimiya, Moscow, p. 315
(1981).
3
-1
-1
2. Ch.K. Rasulov, A.G. Azizov, V. G. Mirzoev, R.K.Azimova, S.I.Abasov
and S.Z. Alieva, Petroleum Chem., 49, 377 (2009);
1
230 and 1190 cm refer to valence vibrations of P-O-C bonds.
PMR spectrum of tri[p-(cyclohexenyl)phenyl]phosphite
https://doi.org/10.1134/S0965544109050065.
consists of three signals of resonance adsorption: singlet in the
3. V.G. Mirzayev, Process. Petrochem. Oil Refining, 17, 93 (2015).