Title of Invention

"AN IMPROVED PROCESS FOR THE PRODUCTION OF BENZOPHENONE OR SUBSTITUTED BENZOPHENONES"

Abstract This invention relates to an improved process for the preparation of benzophenone or substituted benzophenones of the formula (1) where R represents H or CH3 which comprises reacting benzene or substituted benzene with solution of a benzoylating agent in organic solvent in the presence of a solid crystalline microporous catalyst composite material consisting of alumino silicate having molar composition in anhydrous state as follows: M/n : A1O2 : zSiO2 (where M is portion or alkali or alkaline or rare earth metal with valency n and z is between 2-500) having SiO2/A12O3 molar ratio of from 2-50 and a pore size of 5-10 Ao at a temperature in the range of 5-150°C at aatmospheric pressure for a period in the range of 1-24 hours and recovering the benzophenone and or substituted benzophenones from the reaction products by conventional methods.
Full Text The present invention relates to an improved pro for the production of benzophenones or substituted benzophenones. More particularly, the invention relates to a process for producing benzophenone and methyl-benzophenones, represented by the formula 1 shown in the drawing accompanying this specification,
where R is H or CH in high selectivity at para posi-
3
tion with the use of benzoyl chloride and a zeolite catalyst. Benzophenone and methylbenzophenones in particular are used mainly as photoinitiators for UV-curable printing inks and coatings. They are employed in the perfume industry as a fixative and as a fragrance with a flowery note and also as intermediates in the preparation of agricultural chemicals. In the prior art, benzophenone is usually produced by atmospheric oxidation of diphenylmethane in the presence of metal catalysts such as copper naphthenate ( Universal Oil Products Co., US pat. 3642 906, 1969; Nippon Shokubai Kagaku, Jap. Pat. 59 219 248, 1983). Other processes include Friedel-Crafts acylation of benzene with benzoyl chloride or of benzene with phosgene (BASF, DT 403 507, 1920) .
There are several processes or methods available in the prior art for the production of methylbenzophenones from toluene. In one method, methylbenzophenones

isomers were obtained by the benzoylation of toluene with benzoyl chloride using Nafion-H catalyst (G.A. .Olah et al. Synthesis p. 672, 1978). The method disclosed in this report has the disadvantage of only achieving low Para/Ortho isomer ratio (3.32) . In another method (G.A. Olah et al. JACS, 93, 6964, 1971) benzoylation of toluene with benzoyl chloride is described. The reaction is carried out in the
presence of a lewis acid catalyst, AlCl . The main
,3
drawback of this homogeneous reaction is the use of stoichiometric amount of catalyst. operational problems, corrosion and separation of the catalyst. In another report (Applied Catalysis, 59, 197, 1990), liquid phase benzoylation of toluene with benzoyl chloride is disclosed using solid superacid of
2-sulphate supported alumina (SO /Al 0 ). Further,
4 2 3
this method has disadvantage of only achieving lower
conversion of benzoyl chloride (46 wt.%) and lower
Para/Ortho ratio (3.17) of methyl benzophenones.
Several types of insolube heterogeneous acid
catalysts have recently been proposed for liquid phase
reactions, to replace the conventional heterogeneous
catalysts such as AlCl and sulphuric acid, which often
3
pose difficult operational problems of corrosion,

catalyst removal from the product and requirement of a
stoichiometric amount of catalyst.
In all the methods described above, some of them
are hazardous and difficult to handle. In some cases,
catalyst is consumed during the reaction and in some
cases catalysts are less active.
Accordingly, it is an object of the present invention to provide an improved process for producing benzophenone and para-methylbenzophenone in high selectivity at higher conversion level by benzoylation of benzene and toluene, respectively, in the presence of a zeolite catalyst.
Another object of the present invention is to obviate the drawbacks and limitations of the prior-art process by providing an improved process for the production of substituted benzophenones from benzene and toluene.
Yet another object of the invention is to provide an improved process which operates at a relatively low temperature. Still another object of this present invention is to provide an improved process which makes use of non-hazardous solid zeolite catalyst. A further object of the invention is to provide an improved process which leads to high yields of ketones resulting from high conversion and high selectivities.
4

Still another object of the invention is to provide an improved process which is safe, not being prone to explosions.
Accordingly, the present invention provides an improved process for the preparation of benzophenone or substituted benzophenones of the formula (1) where R
represents H or CH which comprises reacting benzene or
3
substituted benzene with solution of a benzoylating
agent in organic solvent in the presence of a solid
crystalline microporous catalyst composite material
consisting of alumino silicate having molar composition
in anhydrous state as follows: M/n : AlO2 : SiO2

(where M is proton or alkali or alkaline or rare earth
metals with valency n and z is between 2-500) having
5i0 /Al O molar ratio of from 2-50 and a pore size of 2 2 3
o 5-10 Ao at a temparature in .the range of 5-150 C at
atmospheric pressure for a period in the range of 1-24 hours and recovering the benzophenone and or substituted benzophenones from the reaction products by conventional methods.
It has been found that the object of the present invention can be attained by using microporous alumino-silicate zeolites as catalyst. .In accordance with the process of the present invention benzene and toluene

can be converted to benzophenone and 4-methyl benzophe-none, respectively in the presence of a zeolite catalyst composite material alumino silicate, using solution of a benzoylating agent with stirring in a batch
o reactor at temperatures ranging between 5 to 150 C.
In the process of the present invention, preferably a zeolite having a SiO /Al O molar ratio of 3 to
2 2 3
100 and a pore size of from 5 to 10 Ao is used as the
catalyst .
When a zeolite with a SiO /Al 0 " molar ratio or a ~
2 2 3
pore size being outside the above mentioned range, is used, the formation of benzophenone and para selectivity for 4-methylbenzophenone will be substantially poor. According to the present invention, it is also possible to employ a synthetic zeolite or natural zeolite. Further the ion exchageable cations contained in such zeolites may be usually sodium or potassium, but may further include other cations such as rare earth metals. The cations may be of the same type or of two or more different types.
Benzene and toluene which are employed in the process of the present invention as the starting material are desired to be high in purity. Benzoylating agent used in the present invention contains less than 5% benzoic acid. In order to make the reaction to proceed smoothly and to obtain good results, the amount of benzene/or toluene is preferred to be 1 to 10 times

(by weight) that of benzoylating agent. In the present invention, benzoyl chloride may be added to react with benzene/or toluene in a manner as follows: 1) benzoylating agent is first added to the reaction mixture and then temperature raised. 2) benzoylating agent is added continuously dropwise upto 2 hours. 3) The reaction mixture is heated upto 80oC and benzoylating agent is added dropwise continuously upto 2.5 hours. The first embodiment is effective to get ketones from benzene/toluene. The time required for the benzoylation of benzene and toluene is within a range of 0.5 to 24 hours and may be within a range of 1 to 8 hours under more preferable reaction conditions. After completion of the benzoylation reaction the reaction solution cooled to room temperature and analyzed with gas chromatograph.
To conduct benzoylation of a toluene in accordance with the process of the present invention, for instance, the zeolite, benzene/toluene and a benzoylating agent is introduced in to the mixture in a liquid phase while stirring the mixture at a temperature of not higher than the boiling point. In this operation, a reaction solvent may be employed as the case requires. As the benzoylating agent, there may be employed any agent commonly employed for -• benzoylation of aromatic rings. Preferred are Benzoyl chloride, benzoic anhyride and benzoic acid. These benzoylating agent may

be employed as diluted with an inert gas such as nitrogen. The reaction temperature for the benzoylation is usually from OoC to the boiling point of the reaction mixture, preferably from 5o-150oC. The reaction may be conducted under reduced or elevated pressure, but is usually conducted under atmospheric pressure. According to the process of the present invention, it is possible to selectively and efficiently benzoyi-ate the para-position of the toluene while suppressing the benzoylation at the ortho and meta position. The advantages of the process of the present invention
1. The process of the present invention shows remarkably high industrial merits over prior art process for the preparation of benzophenone and 4-methyl benzophe-none. The starting materials are easely available and easy to handle and that ketones can be produced in high yield by extremely simple operation.
2. Another advantageous feature of the process of the present invention is that the reaction is carried out at relatively low temparature between 5o and 150oC.
3. A yet another advantageous feature of the process of the present invention is the use of the non-hazardous solid alumino silicate catalyst.
4. Another important and advantageous feature cf the process of the present invention is that it does not pose risks of explosion.

5. The most important and advantageous feature of the process of the present invention is that both the yields and the selectivities to para-substituted benzo-phenone are very high.
6. The use of zeolite as the catalyst in the liquid phase organic reactions of the present invention provides the following advantages:

a) Easy separation of products from solids by means of a simple procedure of filtration.
b) Adsorption or inclusion of substrate and reagent molecules in to the small pores of solids with nanometer dimensions organizes the molecules in close proximity to lower the activation entropy of the reaction.
c) The co-existing acid and base sites on zeolites accelerate organic reactions synergistically; simultaneous activation of an electrophile and a nucleophile on an acid site and a base site, respectively becomes possible.
d) We;ll defined crystalline structure, uniform micro cavitie:s effecting selective reactions of organic molecules incorporeted therein under steric restriction.
e) High cation-exchangeability to ensure easy adjustment of their acidic and basic properties in a wide range of acidity.
The present invention is described in further detail with reference to the following examples which

should not be however construed to limit the scope of the prepsent invention in any manner whatsoever.
Example 1
This example illustrates the procedure for the
conversion of benzene to benzophenone. 50 g benzene
and 40 g benzoyl chloride were taken in a pot reactor.
3 g of the catalyst composite material zeolite H-Beta
was added to the reaction mixture. The reaction mix-
o ture was heated up to 80 C with stirring. The reaction
was continued for 5 hours and the reaction mixture
cooled to room temparature and analyzed with gas-chro-
matograph. The results are recorded in Table 1.
Table-1. Benzoylation of benzene with benzoyl chloride
over catalyst composite material alumino
silicate ( zeolite H- Beta) after 5 hours.
Benzoyl chloride conversion (wt%) 24.7
Product yields (wt%)
benzophenone 24.7
Example 2 This example illustrates the effect of reaction time on the conversion of benzoyl chloride into benzophenone. 50 g of benzene and 40 g of benzoyl chloride were taken in the pot reactor and 3 g of the catalyst

(zeolite H-Beta) was added thereto. The reaction was
o carried out at 80 C under stirring. After the reaction
the reaction mixture was cooled to room temperature and products were analysed by conventional gas-chromatographic method. The results are presented in Table 2 .
Table-2. Effect of reaction time on the conversion of benzoyl chloride in the benzoylation of benzene with benzoyl chloride over catalyst composite material alumino silicate zeolite H- Beta.
(Table Removed)
Example 3 This example illustrates the procedure for the conversion of benzene to benzophenone. 50g benzene and 40 g benzoyl chloride were taken in a pot reactor. 3g of the catalyst composite material rare earth exchanged
alumino silicate (RE-Y) was added to the reaction
o mixture. The reaction mix" was heated up to 80 C
with stirring. The reaction was continued for 18 hours
and the reaction mixture cooled to room temperature and

analyzed with gas chromatograph. The results are recorded in Table 3.
Table-3.Benzoylation of benzene with benzoyl chloride over catalyst composite material rare earth alumino silicate (RE-Y) after 18 hours.
(Table Removed)
Example 4 This example illustrates the effect of reaction time on the conversion of benzoyl chloride into benzophenone. 50 g of benzene and 40 g of benzoyl chloride were taken in the pot reactor and 3 g of the catalyst
(rare earth exchanged alumino silicate, RE-Y) was added
o thereto. The reaction was carried out at 80 C under
stirring. After the reaction, the reaction mixture was
cooled to room temperature and products were analyzed
by conventional gas chromographic method. The results
are presented in Table-4.
Table-4. Effect of reaction time on the conversion of benzoyl chloride in the benzoylation of benzene with benzoyl chloride over rare earth exchanged catalyst composite material alumino silicate RE-Y.

(Table Removed)
Example 5 This example illustrates the procedure for the reaction of toluene and benzoyl, chloride to 2-methyl-, 3-methyl-, 4-methyl benzophenone and dibenzoyltoiuene (others). 60 g toluene, 30 g benzoyl chloride and 4 g catalyst composite material, rare earth cation exchanged aluminosilicates (RE-Y), were taken in the
flask. The reaction mixture was stirred and heated up
o to 110 C in the presence of nitrogen gas/ After the
completion of the reaction the reaction mixture cooled
to room temperature and aanalyzed with gas-chromato-
graph. The results are recorded in Table 5.
Table-5. Benzoylation of toluene with benzoyl chloride over catalyst composite material rare earth cation exchanged alumino silicate, RE-Y, after 18 hours.
(Table Removed)
Examp1e 6 This example illustrates the effect of reaction time on the conversion of benzoyl chloride into 2-methyl-, 3-methyl-, 4-methylbenzophenone and others (dibenzoyltoluene) . The reaction was carried out in a four necked flask (capacity 250 ml), one neck was fitted with a condenser, another with a thermometer, third with the nitrogen gas line and fourth with a rubber septum. 6.0 g toluene, 30 g benzoyl chloride and 4 g catalyst rare earth exchanged composite material aluminosilicate, RE-Y, weire taken in the flask. the reaction mixture was stirred and heated up to the desired' temperature in the presence of nitrogen gas. The reaction was monitored by taking product samples periodically. After the completion of the reaction mixture cooled to room temperature and analyzed with gas-chromatograph. The
results are recorded in Table-6.
Table-6. Effect of reaction time on the conversion of benzoyl chloride in the benzoylation of toluene over rare earth -exchanged catalyst composite material aluminosilicate, RE-Y.
(Table Removed)
Example-7 This example illustrates the effect of protonic catalyst (H-Y zeolite) on the conversion of benzoyl chloride to 2-methyl-, 3-methyl-, 4-methylbenzophenone and dibenzoyltol-uene. 60 g toluene, 40 g benzoyl chloride and 5 g catalyst composite material H-Y was when in the flask. The reaction mixture was stirred and heated up to desired temperature in the presence of nitrogen gas. After the completion of the

reaction, the reaction mixture cooled to room temperature and analyzed with gas chromatograph. The results are recorded in Table-7.
Table-7. Effect of H-Y catalyst on the conversion of benzoyl chloride in the benzoylation of toluene after 18 hours.
(Table Removed)
Example 8 This example illustrates the effect of reaction time on the conversion of benzoyl chloride into 2-methyl-, 3-methyl, 4-methylbenzophenones using zeolite H-Y. 60 g toluene, 40g benzoyl chloride and 5 g catalyst composite material. Zeolite; H-Y were taken in the flask. The reaction mixture was stirred and heated up to desired temperature in the presence of nitrogen gas. After the completion of the 3action, the reaction n.xture cooled to room . temperature and analyzed with gas chromatograph. The results are recorded in Table-8.

Table-8.Inf1 uence of reaction time on the conversion of benzoyl chloride in the benzoylation of toluene over catalyst composite material, zeolite H-Y.
(Table Removed)
Example 9 This example illustrates the procedure for the reaction of toluene and benzoyl chloride to 2-methyl-, 3-methyl-, 4-methylbenzophenones and dibenzoyltoluene (others). 60 g toluene, 30 g benzoyl chloride and 4 g catalyst composite material, aluminosilicate (zeolite H-Beta), were taken in
the flask. The reaction mixture was stirred and heated up
o to 110 C in the presence of nitrogen gas. After the completion of the reaction, the reaction mixture cooled to room temperature and analyzed with gas-' chromatograph. The results are recorded in Table 9.
TabIe-9. Benzoylation of toluene with benzoyl chloride over catalyst composite material, alummosiiicate, zeolite H-Beta after 3 hours.
(Table Removed)
Example 10 This example illustrates the effect of reaction time on the conversion of benzoyl chloride into 2-methyl-, 3-methyl-, 4-methylbenzophenones and others (dibenzoyltoluene). The reaction was carried out in a four necked flask (capacity 250 ml), one neck was fitted with a condenser another with a thermometer, third with the nitrogen gas line and fourth with a rubber septum. 60 g toluene, 3 0g benzoyl chloride and 4 g catalyst composite material aluminosilicate, zeolite H-Beta, were taken in the flask. The reaction mixture was stirred and heated up to the desired temperature in the presence of nitrogen gas. The reaction was monitored by taking product samples periodically. After the completion
of the reaction, the reaction mixture cooled to room temperature and analyzed with gas-chromatograph. The results are recorded in Table-10.
Table-10. Effect of reaction time on the conversion of benzoyl chloride in the benzoylation of toluene over catalyst composite material aluminosilicate. zeolite H-Beta.
(Table Removed)
Example 11
This example illustrate the influence of reaction
temperature on the conversion of benzoyl chloride into 2-
meyhyl-, 3-methyl-, 4-methylbenzophenone and dibenzoyltol-
uenes. 3 0 g toluene, 20 g benzoyl chloride and 2 g catalyst
composite material, rare each cation exchanged microporous
aluminosilicate. RE-Y were taken in the reaction flask.
o The reaction mixture was heated up to 70 C with stirring.

The reaction was continued for 24 hours and the reaction
mixture cooled to room temperature and analyzed with gas
o chromatograph. The results obtained in this example at 80 C
were compared with the results obtained in example 4 at
o 110 C.
Table-11. Influence of reaction temperature on the conversion of benzoyl chloride in the benzoylation of toluene
over rare earth catalyst composite material aluminosili-
(Table Removed)
Example 12 This example illustrates the effect of zeolite catalyst on the; conversion of benzoyl chloride into 2-methyl-, 3-methyl- and 4-methylbenzophenones. 60 g toluene, 3 0 g benzoyl chloride and 4 g catalyst composite material, zeolite H-ZSM-5, was taken in the flask. The reaction mixture
o was stirred and heated upto 110 C in the presence of nitro-
gen gas. After the completion of the reaction, the reaction mixture cooled to room temperature and analyzed with gas chromatograph. The results are recorded in Table 12.
Table-12. Benzoylation of toluene with benzoyl chloride over catalyst composite material, H-ZSM-5 after 18 hrs.
(Table Removed)
Example 13
This example describes the influence of zeolite, H-ZSM-12, on the conversion of benzoyl chloride to 2-methyl-, 3-methyl-, 4-methylbenzophenones in the benzoylation of toluene. 40 g toluene, 20 g benzoyl chloride and 3 g catalyst
composite material zeolite H-ZSM-12 was taken in the flask.
o The reaction mixture was stirred and heated upto 110 C in
the presence of nitrogen gas. After the completion of the
reaction, the reaction mixture cooled to room temperature
and analyzed with gas chromatograph. The results are re-

corded, m Table 13 .
Table-13. Benzoylation of toluene with benzoyl chloride
over catalyst composite material zeolite H-ZSM-5 18 hrs.
(Table Removed)
Example 14
This example illustrates the effect of zeolite H-
Mordenite on the conversion of benzoyl chloride to 2-methyl-
3-methyl-, 4-methylbenzophenones. 60 g toluene,-- 30 g
benzoyl chloride and 4 g catalyst composite material, H-
mordenite, was taken in the flask. The reaction mixture was
o stirred and heated upto 110 C in the presence of nitrogen
gas. After the completion of the reaction the reaction
mixture cooled to room temperature and analyzed wtth gas
chromatograph. The results are presented in Table 14.
Table-14. Benzoylation of toluene by benzoyl chloride over catalyst composite material, H-Mordenite after I8h.
(Table Removed)
Example 15
This example illustrates the effect of zeolite H-ZSM-5
on the conversion of benzoyl chloride into benzophenone. 50
g benzene and 4 0 g benzoyl chloride were taken in the pot
reactor and 3 g of the catalyst, H-ZSM-5, was added thereto.
o
The reaction was carried out at 80 C under stirring. After
the reaction, the mixture was cooled to room temperature and products were analyzed by conventional gas chromatographic method. The results are presented in Table 15.
Table-15. Benzoylation of benzene with benzoyl chloride over catalyst composite material H-ZSM-5 after 18h.
(Table Removed)
Example 16 This example illustrates the influence of zeolite H-ZSM-12 on the conversion of benzoyl chloride into benzophenone. 50 g benzene and 40 g of benzoyl chloride were
taken in the pot reactor and 3 g of the catalyst, H-Z5M-12,
o was added thereto. The reaction was carried out at 80 C
under stirring. The reaction mixture was cooled to room
temperature and products were analyzed by conventional gas
chromatographic method. The results are listed in Table 16.
Table 16. Benzoylation of benzene with benzoyl chloride over catalyst composite material, H-ZSM-12, after 18h.
(Table Removed)

Example 17
This example illustrates the effect of benzoylating
agent on the formation of benzophenone. 50 g benzene and 30
g benzoic anhydride were taken in the reaction flask. 5 g of
the catalyst composite material zeolite H-beta was added to
the reaction mixture. The reaction mixture was heated up to
o 80 C with stirring. The reaction was continued for 10 hours
and the reaction mixture cooled to room temperature and
analyzed with gas-chromatograph. The results are recorded in
Table 17.
Table-17 Benzoylation of benzene with benzoic anhydride over catalyst composite material aluminosilicate (zeolite H-beta) after 10 hours.
(Table Removed)
Example-18
This example illustrates the effect of benzoylating agent on the formation of methylbenzophenones. The reaction was carried out in a four necked flask (capacity 250ml), one neck was fitted with a condenser another with a thermometer

third with the nitrogen gas and fourth with a rubber septum. 60 g toluene, 40 g benzoic anhydride and 5 g catalyst composite material H-beta was taken-in the flask. The reaction mixture was stirred and heated up to desired temperature in the presence of nitrogen gas. After the completion of the reaction, the reaction mixture cooled to room temperature and analyzed with gas-chromatography The results are recorded in Table 18.
Table-18 Benzoylation of toluene with benzoic anhydrrde over catalyst composite material, aluminosilicate (zeolite H-beta) after 18 hours.
(Table Removed)




WE CLAIM :
1. An improved process for the preparation of benzo
phenone or substituted benzophenones of the formula
(1) where R represents H or CH which comprises react-
3
ing benzene or substituted benzene with solution of a
benzoylating agent in organic solvent in the presence
of a solid crystalline microporous catalyst composite
material - consisting of alumino silicate having molar
composition in anhydrous state as follows: M/n : AlO
2
: zSiO (where M is proton or alkali or alkaline or 2
rare earth metals with valency n and z is between 2-
500) having SiO /Al 0 molar ratio of from 2-50 and a
2 2 3
pore size of 5-10 Ao at a temparature in the range of
o 5-150 C at atmospheric pressure for a period in the
range of 1-24 hours and recovering the benzophenone and
or substituted benzophenones from the reaction products
by conventional methods.
2. An improved process as claimed in claim 1 wherein
the solid crystalline microporous catalyst composite
material used is zeolite tt v or zeolite H-Y or zeo
lite H-Beta.

3. An improved process as claimed in claims 1 & 2
wherein the organic solvent used is CHCl or CC1 or 1,2-
3 4
dichloroethane or nitrobenzene or mixture thereof.
4. An improved process as claimed in claims 1 to 3 wherein the benzoylating agent used is benzoyl chloride, benzoic acid or benzoic anhydride.
5. An improved process as claimed in claims 1 to 4 wherein the ratio of benzene or toluene to the benzoylating agent is in the range of 1 to 10 by weight.
6. An improved process for the preparation of benzo-phenone or substituted benzophenones of the formula (1) substantially as herein before described with reference to the examples.

Documents:

289-del-1995-abstract.pdf

289-del-1995-claims.pdf

289-del-1995-correspondence-others.pdf

289-del-1995-correspondence-po.pdf

289-del-1995-description (complete).pdf

289-del-1995-form-1.pdf

289-del-1995-form-2.pdf

289-del-1995-form-4.pdf

289-del-1995-form-9.pdf

abstract.jpg


Patent Number 190725
Indian Patent Application Number 289/DEL/1995
PG Journal Number 31/2009
Publication Date 31-Jul-2009
Grant Date 15-Mar-2004
Date of Filing 22-Feb-1995
Name of Patentee COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH
Applicant Address RAFI MARG, NEW DELHI-110001, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 DEBASIS BHATTACHARYA NATIONAL CHEMICAL LABORATORY PUNE 411008, MAHARASTRA, INDIA.
2 SUJIT BARUN KUMAR NATIONAL CHEMICAL LABORATORY PUNE 411008, MAHARASTRA, INDIA.
3 ANAND PAL SINGH NATIONAL CHEMICAL LABORATORY PUNE 411008, MAHARASTRA, INDIA.
4 PAUL RATNASAMY NATIONAL CHEMICAL LABORATORY PUNE 411008, MAHARASTRA, INDIA.
PCT International Classification Number C07C 15/12
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA