International Journal of Mechanical Engineering and Technology (IJMET)

Volume 9, Issue 13, December 2018, pp. 233–236, Article ID: IJMET_09_13_025
Available online at http://www.iaeme.com/ijmet/issues.asp?JType=IJMET&VType=9&IType=13
ISSN Print: 0976-6340 and ISSN Online: 0976-6359

© IAEME Publication Scopus Indexed

NEW METHOD OF BENZOCYCLOBUTENE SYNTHESIS FOR

MATERIALS WITH LOW DIELECTRIC PERMEABILITY FOR
MICROELECTRONICS
P.A. Chicheva, K.S. Levchenko and K.A. Chudov
Federal State Budget Educational Institution of Higher Education «MIREA – Russian
Technological University», Vernadskogo pr., 78, 119454, Moscow, Russian Federation,

P.S. Shmelin
JSC «TECHNOMASH», I. Franko str., 4, 121108, Moscow Russian Federation,

ABSTRACT
In this paper, a new method of benzocyclobutene synthesis was described. The
developed techniques allow to obtain benzocyclobutene from cheap components, which
subsequently will significantly reduce the cost of production of benzocyclobutene-based
composite compositions. Benzocyclobutene derivatives in electronics and
microelectronics can be important for creation of insulating structures in silicon, gallium
arsenide, and ceramic devices, micromotor and microgenerator devices, for isolation of
laser structures in quantum cascade lasers, insulating layers in multifunctional high-
density electronic modules, coatings of high-frequency printed circuit boards for
telecommunications, photoresists for plasma chemical and ion etching and oth.
Keywords: benzocyclobutene, materials with low dielectric permeability, insulating
materials, microelectronics
Cite this Article: P.A. Chicheva, K.S. Levchenko, K.A. Chudov and P.S. Shmelin, New
Method of Benzocyclobutene Synthesis for Materials with Low Dielectric Permeability for
Microelectronics, International Journal of Mechanical Engineering and Technology,
9(13), 2018, pp. 233–236
http://www.iaeme.com/IJMET/issues.asp?JType=IJMET&VType=9&IType=13

1. INTRODUCTION
High interest in materials based on benzocyclobutene (BCB) is explained by a complex of unique
physicochemical properties: low dielectric constant (2.65), high breakdown voltage (5.3 MV /
cm), high thermal stability (weight loss <1.7% / h at t = 350 ° C), low moisture absorption,
combined with good mechanical properties (tensile strength, modulus of elasticity, elongation at
break). New photo- and thermocurable materials based on benzocyclobutene derivatives in
electronics and microelectronics can be important for creation of insulating structures in silicon,
gallium arsenide, and ceramic devices, micromotor and microgenerator devices, for isolation of
laser structures in quantum cascade lasers, insulating layers in multifunctional high-density
electronic modules, coatings of high-frequency printed circuit boards for telecommunications,
photoresists for plasma chemical and ion etching and oth. [1-3].

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 P.A. Chicheva, K.S. Levchenko, K.A. Chudov and P.S. Shmelin

2. MATERIALS
Nitrotoluene (Sigma Aldrich, USA), bromine (Sigma Aldrich, USA), hydrobromic acid (Sigma
Aldrich, USA), butyl lithium (Sigma Aldrich, USA), butyl nitrite (Sigma Aldrich, USA), distilled
water, hexane (Base of reagents No. 1 , Russia), dimethyl sulfoxide (Reagent Base No. 1, Russia),
sodium carbonate (Reagent Base No. 1, Russia), paraform (China), ammonium peroxodisulfate
(Sigma Aldrich, USA), hydrochloric acid conc. (Base of reagents No. 1, Russia), sodium sulfate
(Sigma Aldrich, USA), tetrahydrofuran (China), sodium phenolate (Sigma Aldrich, USA),
calcium chloride (Sigma Aldrich, USA), zinc granulated (Sigma Aldrich, USA), carbon
tetrachloride (Sigma Aldrich, USA), ethanol (Reagent Base No. 1, Russia), ethyl acetate (Reagent
Base No. 1, Russia).
3. EXPERIMENTAL
2-Nitrophenethyl alcohol. 2-Nitrotoluene (92 g, 0.67 mol), sodium phenolate (0.6 g, 5.6 mmol),
paraform (9 g) and DMSO (200 ml) were stirred for 1 hour at 60-67 ° C. The mixture was poured
into water, extracted with ethyl acetate, the organic phase was washed with water, dried over
sodium sulfate. The solvent was evaporated in vacuum. The product was isolated by vacuum
distillation (140 ° C / 0.1 mmHg). Yield 56 g (63%).
2- (2-Aminophenyl) ethanol. Method A. 2-Nitrophenethyl alcohol (12 g, 71.8 mmol) was
added to a mixture of calcium chloride (4.8 g, 43.2 mmol), zinc dust (16 g, 615 mmol) in hot
water (100 ml). The mixture was boiled under stirring for 30 minutes, then filtered. Sodium
carbonate (4.8 g, 45.3 mmol) was added to the filtrate, the water was evaporated under vacuum,
the residue was dissolved in ethyl acetate, the salts were filtered off, the filtrate was evaporated
under vacuum. Yield 8.7 g (88%).
2- (2-Aminophenyl) ethanol. Method B. 2-Nitrophenethyl alcohol (1.67 g, 10 mmol) and 3
g of iron powder were dissolved in ethyl alcohol, a few drops of concentrated hydrochloric acid
were added to the solution and the mixture was boiled until the starting 2-nitrophenethyl alcohol
disappeared (TLC control). After completion of the reaction, the precipitate was filtered and
washed with hot ethyl alcohol. The filtrate was evaporated under vacuum. Yield 72%. The
product was used in the next step without further purification.
1- (2-Bromoethyl) -2-aminobenzene hydrobromide. K2- (2-aminophenyl) ethanol (4.8 g,
34.8 mmol) was added hydrobromic acid (50 ml, 48% aq. P) and stirred at reflux for 4 hours. The
precipitate was filtered, washed with hydrogen bromide. The output 5.6 g (80%). The product
was used in the next step without further purification.
1-Bromo-2- (2-bromoethyl) benzene. To a solution of 1- (2-bromoethyl) -2-aminobenzene
(5.6 g, 20 mmol) of hydrobromide in absolute ethanol (60 ml) butyl nitrite (14 ml, 60 mmol) was
dropped in at -5-0 ° C. The diazonium salt was filtered, washed with ethyl acetate. A mixture of
carbon tetrachloride (60 ml), bromine (3.2 g, 20 mmol) and ammonium peroxodisulfate (0.2 g,
8.8 x 10-1 mmol) was boiled for 15 minutes, after which the diazonic salt was added in portions
in THF, after which the mixture was boiled at stirring for 15 minutes. The solvent was evaporated
under vacuum, the product was extracted with ethyl acetate, washed with water, dried over
sodium sulfate, the solvent was evaporated. The product was purified by vacuum distillation (67-
68 ° C / 0.2 mmHg). Yield 2.9 g (56%).
Benzocyclobutene. A solution of butyl lithium (4.5 ml, 2.5 M in hexane) was added dropwise
to a solution of 1-bromo-2- (2-bromoethyl) benzene (2.9 g, 11.2 mmol) in anhydrous THF at -70
° C. The solution was stirred for 30 minutes at -70 ° C, then gradually brought to room
temperature, leaving stirring for another 1 hour. The mixture was poured into water, after standard
treatment the solvent was evaporated. The product was purified by vacuum distillation (47-50 °
C / 20 mmHg).
All the products obtained were characterized by 1 H, 13 C NMR and mass spectroscopy.

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 New Method of Benzocyclobutene Synthesis for Materials with Low Dielectric Permeability for
Microelectronics

4. RESEARCH AND DISCUSSION

The method is based on multistage laboratory synthesis from cheap raw materials, such as
nitrotoluene, paraform, sodium phenoxide, DMSO, etc. and makes it possible to obtain a hard-
to-reach limiting precursor, 2-bromophenethyl bromide, which gives the target benzocyclobutene
in high yields under lithiation conditions. The synthesis scheme is shown in Figure 1.

OH OH Br

NO2 PhONa NO2 Zn, NH2 NH2*HBr

(CH2O)n CaCl2 HBr

DMSO

Br Br

Br
+ N
N Br n-BuLi
C4H9ONO Br2, (NH4)2S2O8
-70oC

Figure.1 Scheme of benzocyclobutene synthesis

In the first stage, 2-nitrophenethyl alcohol was isolated by heating 2-nitrotoluene and
paraform in the presence of catalytic amounts of sodium phenolate in DMSO medium at a
temperature of 60-67 °C. This reaction was studied under conditions of catalysis by various bases,
such as sodium phenolate, NaOH, KOH, quaternary ammonium salts, alkali metal carbonates,
and also under conditions of polar proton and aprotic solvents such as EtOH, DMSO, DMF. It
was found that the most successful combination was the use of potassium phenolate in DMSO
medium when heated to 60-70 ° C and using KOH in DMF medium when heated to 80 ° C. The
target product was isolated with a yield of 63%.
In addition to the 2-nitrophenethyl alcohol, a high boiling point reformylation product is
formed as a by-product. Purification was carried out by distillation under reduced pressure, since
the heating of nitrophenethyl alcohol above 190 ° C leads to its decomposition and a significant
decrease in the yield and purity of the distillate.
The reduction of 2-nitrophenethyl alcohol can be carried out in different ways. As part of this
work, the reduction in the presence of zinc and calcium chloride in an aqueous medium was used,
as well as the reduction in alcohol in the presence of metallic iron. Both methods give good
results. The preparation of 2-aminophenethyl bromide was carried out by boiling in concentrated
hydrobromic acid for 4 hours.
The preparation of 2-bromophenethyl bromide was carried out using a modified Sandmeer
reaction. To this end, the diazonium salt of (2-bromoethyl) benzene, obtained by adding butyl
nitrite to 1- (2-bromoethyl) -2-aminobenzene in absolute ethanol, was added in portions to a
solution of bromine and ammonium peroxydisulfate in a solution of carbon tetrachloride.
The reaction proceeds by a radical mechanism, as evidenced by the fact that the reaction does
not proceed when heated in the absence of a radical initiator of ammonium persulfate. The target
benzocyclobutene was obtained by intramolecular cyclization of the lithium salt of
bromethylbenzene. The reaction takes place at a temperature of -70 ° C with good yields (70-
75%).

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 P.A. Chicheva, K.S. Levchenko, K.A. Chudov and P.S. Shmelin

5. CONCLUSIONS
So, in this paper new method for the synthesis of benzocyclobutene was developed. The
developed techniques allow to obtain benzocyclobutene from cheap components, which
subsequently will significantly reduce the cost of production of benzocyclobutene-based
composite compositions.
Analysis of the use of materials based on benzocyclobutene showed that the potential use of
benzocyclobutene is almost unlimited: in addition to using materials based on it as dielectric
insulating layers, it can be functional materials for OLED devices [4-6], optical waveguide
materials [7], materials for implants with high biocompatibility and chemical resistance.
Introduction of benzocyclobutene fragments into polymer chains of polymers already widely
used in various industrial processes.

ACKNOWLEDGMENTS
The work was financially supported by a grant from the Ministry of Science and Higher
Education of the Russian Federation (Scientific project “Development of new heat-resistant
materials with low dielectric constant for microelectronics based on o- and p-xylylenes
derivatives produced from benzocyclobutene and cyclophane”) Agreement on granting a subsidy
from the Ministry of Science and Higher Education of the Russian Federation dated September
26, 2017, No. 14.577.21.0273, Unique identifier of PNIER RFMEFI57717X0273).

REFERENCES
[1] H. Arbess, F.Baccar, L. Theolier, S. Azzopardi, E. Woirgard Mechanical stress investigation
after technological process in Deep Trench Termination DT2 using BenzoCycloButene as
dielectric material // Microelectronics Reliability – 2015 - № 55(9–10) – С. 2017-2021;
[2] S. Ruzgar, M. Caglar Use of bilayer gate insulator to increase the electrical performance of
pentacene based transistor // Synthetic Metals – 2017 - №232 – С. 46-51;
[3] B.W. D'Andrade, A.Z. Kattamis, P.F. Murphy // Handbook of Flexible Organic Electronics –
2015- С.315-341;
[4] B.W. Ma, F. Lauterwasser, L. Deng, C.S. Zonte, B.J. Kim, J.M. Frechet, // J. Chemistry of
Materials – 2007 -№19 – С.4827-4832;
[5] H.-J. Lee, J.-K. Jeong, S.Y., G. Mo // Патент США №8598781 - 2013;
[6] C.A. Zuniga, J. Abdallah, W. Haske, Y. Zhang, I. Coropceanu, S. Barlow, B. Kippelen, S.R.
Marder // Adv. Mater. – 2013 - №25 – С.1739–1744;
[7] L. Cao, A.-S. Grimault-Jacquin, N. Zerounian, F. Aniel Design and VNA-measurement of
coplanar waveguide (CPW) on benzocyclobutene (BCB) at THz frequencies // Infrared
Physics & Technology – 2014 - №63 – С.157-164.

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