CN106478362A - A kind of catalytic preparation process of 4,4 ' dichloride methyl biphenyl - Google Patents
A kind of catalytic preparation process of 4,4 ' dichloride methyl biphenyl Download PDFInfo
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- CN106478362A CN106478362A CN201610743114.4A CN201610743114A CN106478362A CN 106478362 A CN106478362 A CN 106478362A CN 201610743114 A CN201610743114 A CN 201610743114A CN 106478362 A CN106478362 A CN 106478362A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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Abstract
The invention discloses a kind of catalytic preparation process of 4,4' dichloride methyl biphenyl, by biphenyl, mass fraction be 27 37% hydrochloric acid and paraformaldehyde compare 1 according to weight:(3‑4):(0.65 0.85) are put in reactor, add solid catalyst, add organic solvent, be warmed up to 50 80 DEG C, it is passed through HCl gas, after reacting 10 20 hours, reacting liquid filtering is gone out solid catalyst, liquid standing separates sour phase, organic faciess are through washing, crystallizing, being filtrated to get crude product, crude product carries out recrystallization, obtains target product 4,4' dichloride methyl biphenyl.The preparation technology high conversion rate that the present invention provides, solid catalyst can Reusability, and catalytic efficiency no significantly reduces after repeatedly applying mechanically 40 times.
Description
Technical field
The invention belongs to chemical field, it is related to intermediate and in particular to prepared by a kind of catalysis of 4,4'- dichloride methyl biphenyl
Technique.
Background technology
4,4'- dichloride methyl biphenyl abbreviation biphenyl-benzyl dichloride, are a kind of important organic synthesis intermediates, are synthesis fluorescence
Brightening agent FP and the key intermediate of stilbene biphenyl fluorescent brightener CBS.Fluorescent whitening agent is widely used in plastics, fibre
The brightening of dimension, coating etc., it brightens, brightening effect is fairly obvious；It has excellent resistance to oxygen bleaching, chlorine-resistant drift, resistance to strong acid simultaneously
Highly basic performance and excellent perspiration fastness.And its whiteness is very stable, washs, contaminate, dry the loss of process seldom, stores
Not easy to change in journey.Biphenyl-benzyl dichloride also can be used for the synthesis of high-performance resin matrix as a kind of monomer.In addition, it may also be used for
Synthesizing compound of liquid crystal and polymer.
The production technology of biphenyl-benzyl dichloride, currently commonly used both at home and abroad is with biphenyl, paraformaldehyde as raw material, with stone
Oily ether or hexamethylene are solvent, under the effect of catalyst zinc chloride, are passed through HCl gas and carry out chloromethylation.This preparation
Method is simple to operation, and because by-product monochloro methyl biphenyl is more, after refined, yield only has 60% about, and it is sour
Property organic wastewater all the time be puzzlement manufacturer a difficult problem.
Content of the invention
It is an object of the invention to provide a kind of catalytic preparation process of 4,4'- dichloride methyl biphenyl.
The above-mentioned purpose of the present invention is achieved by techniques below scheme：
A kind of catalytic preparation process of 4,4'- dichloride methyl biphenyl：By biphenyl, mass fraction be 27-37% hydrochloric acid and
Paraformaldehyde compares 1 according to weight:(3-4):(0.65-0.85) put in reactor, add solid catalyst, add organic
Solvent, is warmed up to 50-80 DEG C, is passed through HCl gas, after reaction 10-20 hour, reacting liquid filtering is gone out solid catalyst, liquid
Standing separates sour phase, and through washing, crystallizing, being filtrated to get crude product, crude product carries out recrystallization to organic faciess, obtains target product 4,
4'- dichloride methyl biphenyl；Wherein, the preparation method of described solid catalyst comprises the steps：Step S1, deionized water is molten
Solution AlCl3, add glycerol, stir, ammonia adjusts pH value and obtains white precipitate, filter, wash, obtain wet cake；Step S2,
By Zr (NO3)4·5H2O is dissolved in the hydrochloric acid solution of mass fraction 15%-25%, and this hydrochloric acid solution is Zr (NO3)4·5H2O weight
8-12 times；Step S3, by wet cake stirring and dissolving in step S2 resulting solution, obtains mixed solution, evaporation mixed solution obtains
White solid；By white solid and modified Nano Kaolin mixed grinding, the two weight ratio is 1:2-3, then in Muffle
In stove, 500-700 DEG C of calcining 3-5 hour obtains final product described solid catalyst；It is AlCl that glycerol adds weight3Add the 2- of weight
4%；AlCl3With Zr (NO3)4·5H2O mol ratio is 1:0.5-2.5；
Described modified Nano Kaolin preparation method is：Nano kaoline 30-40 part is taken to be scattered in 50-60 part mass fraction
For, in the disodium ethylene diamine tetra-acetic acid aqueous solution of 5-15%, stirring 1-2 hour under the conditions of 40-50 DEG C, adding 5-15 part sulfur
Sour nickel, stirs 20-30min, filters, be drying to obtain after cooling.
Preferably, described modified Nano Kaolin preparation method is：Take 35 parts of nano kaoline to be scattered in 55 parts of quality to divide
In the disodium ethylene diamine tetra-acetic acid aqueous solution for 10% for the number, stir 1.5 hours under the conditions of 45 DEG C, add 10 parts of nickel sulfate,
Stirring 25min, filters after cooling, is drying to obtain.
Preferably, described organic solvent is hexamethylene, adds 3-7 times that quality is biphenyl quality.
Preferably, the addition quality of described solid catalyst is the 10-20% of biphenyl quality.
Preferably, the mole of the HCl gas being passed through is 1.5-2.5 times of biphenyl mole.
Advantages of the present invention：
The preparation technology high conversion rate that the present invention provides, solid catalyst can Reusability, and urge after repeatedly applying mechanically 40 times
Change efficiency no to significantly reduce.
Specific embodiment
Further illustrate the essentiality content of the present invention with reference to embodiment, but present invention protection model is not limited with this
Enclose.Although being explained in detail to the present invention with reference to preferred embodiment, it will be understood by those within the art that, can be right
Technical scheme is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention.
Embodiment 1：The catalysis preparation of 4,4'- dichloride methyl biphenyl
By biphenyl, mass fraction be 32% hydrochloric acid and paraformaldehyde compare 1 according to weight:3.5:0.75 puts into reactor
In, add solid catalyst, add organic solvent, be warmed up to 65 DEG C, be passed through HCl gas, after reacting 15 hours, by reactant liquor
Filter out solid catalyst, liquid standing separates sour phase, through washing, crystallizing, being filtrated to get crude product, crude product carries out weight to organic faciess
Crystallization, obtains target product 4,4'- dichloride methyl biphenyl.Wherein, described organic solvent is hexamethylene, and addition quality is biphenyl matter
5 times of amount；The addition quality of described solid catalyst is the 15% of biphenyl quality；The mole of the HCl gas being passed through is biphenyl
2 times of mole.
Wherein, the preparation method of described solid catalyst comprises the steps：Step S1, deionized water dissolves AlCl3,
Add glycerol, stir, ammonia adjusts pH value and obtains white precipitate, filter, wash, obtain wet cake；Step S2, by Zr
(NO3)4·5H2O is dissolved in the hydrochloric acid solution of mass fraction 20%, and this hydrochloric acid solution is Zr (NO3)4·5H210 times of O weight；Step
Rapid S3, by wet cake stirring and dissolving in step S2 resulting solution, obtains mixed solution, evaporation mixed solution obtains white solid；Will
White solid and modified Nano Kaolin mixed grinding, the two weight ratio is 1:2.5, then in Muffle furnace 600 DEG C forge
Burn and obtain final product described solid catalyst in 4 hours；It is AlCl that glycerol adds weight3Add the 3% of weight；AlCl3With Zr (NO3)4·
5H2O mol ratio is 1:1.5；
Described modified Nano Kaolin preparation method is：Taking 35 parts of nano kaoline to be scattered in 55 parts of mass fractions is 10%
Disodium ethylene diamine tetra-acetic acid aqueous solution in, under the conditions of 45 DEG C stir 1.5 hours, add 10 parts of nickel sulfate, stirring
25min, filters after cooling, is drying to obtain.
Embodiment 2：The catalysis preparation of 4,4'- dichloride methyl biphenyl
By biphenyl, mass fraction be 27% hydrochloric acid and paraformaldehyde compare 1 according to weight:4:0.65 puts into reactor
In, add solid catalyst, add organic solvent, be warmed up to 50 DEG C, be passed through HCl gas, after reacting 20 hours, by reactant liquor
Filter out solid catalyst, liquid standing separates sour phase, through washing, crystallizing, being filtrated to get crude product, crude product carries out weight to organic faciess
Crystallization, obtains target product 4,4'- dichloride methyl biphenyl.Wherein, described organic solvent is hexamethylene, and addition quality is biphenyl matter
3 times of amount；The addition quality of described solid catalyst is the 10% of biphenyl quality；The mole of the HCl gas being passed through is biphenyl
1.5 times of mole.
Wherein, the preparation method of described solid catalyst comprises the steps：Step S1, deionized water dissolves AlCl3,
Add glycerol, stir, ammonia adjusts pH value and obtains white precipitate, filter, wash, obtain wet cake；Step S2, by Zr
(NO3)4·5H2O is dissolved in the hydrochloric acid solution of mass fraction 15%, and this hydrochloric acid solution is Zr (NO3)4·5H28 times of O weight；Step
S3, by wet cake stirring and dissolving in step S2 resulting solution, obtains mixed solution, evaporation mixed solution obtains white solid；Will be white
Color solid and modified Nano Kaolin mixed grinding, the two weight ratio is 1:2, then in Muffle furnace, 500 DEG C of calcinings 5 are little
When obtain final product described solid catalyst；It is AlCl that glycerol adds weight3Add the 2% of weight；AlCl3With Zr (NO3)4·5H2O mole
Than for 1:0.5；
Described modified Nano Kaolin preparation method is：Taking 30 parts of nano kaoline to be scattered in 50 parts of mass fractions is 15%
Disodium ethylene diamine tetra-acetic acid aqueous solution in, stir 2 hours under the conditions of 40 DEG C, add 5 parts of nickel sulfate, stir 20min, fall
Filter after temperature, be drying to obtain.
Embodiment 3：The catalysis preparation of 4,4'- dichloride methyl biphenyl
By biphenyl, mass fraction be 37% hydrochloric acid and paraformaldehyde compare 1 according to weight:3:0.85 puts into reactor
In, add solid catalyst, add organic solvent, be warmed up to 80 DEG C, be passed through HCl gas, after reacting 10 hours, by reactant liquor
Filter out solid catalyst, liquid standing separates sour phase, through washing, crystallizing, being filtrated to get crude product, crude product carries out weight to organic faciess
Crystallization, obtains target product 4,4'- dichloride methyl biphenyl.Wherein, described organic solvent is hexamethylene, and addition quality is biphenyl matter
7 times of amount；The addition quality of described solid catalyst is the 20% of biphenyl quality；The mole of the HCl gas being passed through is biphenyl
2.5 times of mole.
Wherein, the preparation method of described solid catalyst comprises the steps：Step S1, deionized water dissolves AlCl3,
Add glycerol, stir, ammonia adjusts pH value and obtains white precipitate, filter, wash, obtain wet cake；Step S2, by Zr
(NO3)4·5H2O is dissolved in the hydrochloric acid solution of mass fraction 25%, and this hydrochloric acid solution is Zr (NO3)4·5H212 times of O weight；Step
Rapid S3, by wet cake stirring and dissolving in step S2 resulting solution, obtains mixed solution, evaporation mixed solution obtains white solid；Will
White solid and modified Nano Kaolin mixed grinding, the two weight ratio is 1:3, then 700 DEG C of calcinings 3 in Muffle furnace
Hour obtains final product described solid catalyst；It is AlCl that glycerol adds weight3Add the 4% of weight；AlCl3With Zr (NO3)4·5H2O rubs
That ratio is 1:2.5；
Described modified Nano Kaolin preparation method is：Taking 40 parts of nano kaoline to be scattered in 60 parts of mass fractions is 5%
Disodium ethylene diamine tetra-acetic acid aqueous solution in, stir 1 hour under the conditions of 50 DEG C, add 15 parts of nickel sulfate, stir 30min,
Filter after cooling, be drying to obtain.
Embodiment 4：The catalysis preparation of 4,4'- dichloride methyl biphenyl
By biphenyl, mass fraction be 32% hydrochloric acid and paraformaldehyde compare 1 according to weight:3.5:0.75 puts into reactor
In, add solid catalyst, add organic solvent, be warmed up to 65 DEG C, be passed through HCl gas, after reacting 15 hours, by reactant liquor
Filter out solid catalyst, liquid standing separates sour phase, through washing, crystallizing, being filtrated to get crude product, crude product carries out weight to organic faciess
Crystallization, obtains target product 4,4'- dichloride methyl biphenyl.Wherein, described organic solvent is hexamethylene, and addition quality is biphenyl matter
5 times of amount；The addition quality of described solid catalyst is the 12% of biphenyl quality；The mole of the HCl gas being passed through is biphenyl
2 times of mole.
Wherein, the preparation method of described solid catalyst comprises the steps：Step S1, deionized water dissolves AlCl3,
Add glycerol, stir, ammonia adjusts pH value and obtains white precipitate, filter, wash, obtain wet cake；Step S2, by Zr
(NO3)4·5H2O is dissolved in the hydrochloric acid solution of mass fraction 20%, and this hydrochloric acid solution is Zr (NO3)4·5H210 times of O weight；Step
Rapid S3, by wet cake stirring and dissolving in step S2 resulting solution, obtains mixed solution, evaporation mixed solution obtains white solid；Will
White solid and modified Nano Kaolin mixed grinding, the two weight ratio is 1:2.5, then in Muffle furnace 600 DEG C forge
Burn and obtain final product described solid catalyst in 4 hours；It is AlCl that glycerol adds weight3Add the 3% of weight；AlCl3With Zr (NO3)4·
5H2O mol ratio is 1:1.5；
Described modified Nano Kaolin preparation method is：Taking 35 parts of nano kaoline to be scattered in 55 parts of mass fractions is 10%
Disodium ethylene diamine tetra-acetic acid aqueous solution in, under the conditions of 45 DEG C stir 1.5 hours, add 10 parts of nickel sulfate, stirring
25min, filters after cooling, is drying to obtain.
Embodiment 5：The catalysis preparation of 4,4'- dichloride methyl biphenyl
By biphenyl, mass fraction be 32% hydrochloric acid and paraformaldehyde compare 1 according to weight:3.5:0.75 puts into reactor
In, add solid catalyst, add organic solvent, be warmed up to 65 DEG C, be passed through HCl gas, after reacting 15 hours, by reactant liquor
Filter out solid catalyst, liquid standing separates sour phase, through washing, crystallizing, being filtrated to get crude product, crude product carries out weight to organic faciess
Crystallization, obtains target product 4,4'- dichloride methyl biphenyl.Wherein, described organic solvent is hexamethylene, and addition quality is biphenyl matter
5 times of amount；The addition quality of described solid catalyst is the 18% of biphenyl quality；The mole of the HCl gas being passed through is biphenyl
2 times of mole.
Wherein, the preparation method of described solid catalyst comprises the steps：Step S1, deionized water dissolves AlCl3,
Add glycerol, stir, ammonia adjusts pH value and obtains white precipitate, filter, wash, obtain wet cake；Step S2, by Zr
(NO3)4·5H2O is dissolved in the hydrochloric acid solution of mass fraction 20%, and this hydrochloric acid solution is Zr (NO3)4·5H210 times of O weight；Step
Rapid S3, by wet cake stirring and dissolving in step S2 resulting solution, obtains mixed solution, evaporation mixed solution obtains white solid；Will
White solid and modified Nano Kaolin mixed grinding, the two weight ratio is 1:2.5, then in Muffle furnace 600 DEG C forge
Burn and obtain final product described solid catalyst in 4 hours；It is AlCl that glycerol adds weight3Add the 3% of weight；AlCl3With Zr (NO3)4·
5H2O mol ratio is 1:1.5；
Described modified Nano Kaolin preparation method is：Taking 35 parts of nano kaoline to be scattered in 55 parts of mass fractions is 10%
Disodium ethylene diamine tetra-acetic acid aqueous solution in, under the conditions of 45 DEG C stir 1.5 hours, add 10 parts of nickel sulfate, stirring
25min, filters after cooling, is drying to obtain.
Embodiment 6：Comparative example, nano kaoline is not modified
By biphenyl, mass fraction be 32% hydrochloric acid and paraformaldehyde compare 1 according to weight:3.5:0.75 puts into reactor
In, add solid catalyst, add organic solvent, be warmed up to 65 DEG C, be passed through HCl gas, after reacting 15 hours, by reactant liquor
Filter out solid catalyst, liquid standing separates sour phase, through washing, crystallizing, being filtrated to get crude product, crude product carries out weight to organic faciess
Crystallization, obtains target product 4,4'- dichloride methyl biphenyl.Wherein, described organic solvent is hexamethylene, and addition quality is biphenyl matter
5 times of amount；The addition quality of described solid catalyst is the 15% of biphenyl quality；The mole of the HCl gas being passed through is biphenyl
2 times of mole.
Wherein, the preparation method of described solid catalyst comprises the steps：Step S1, deionized water dissolves AlCl3,
Add glycerol, stir, ammonia adjusts pH value and obtains white precipitate, filter, wash, obtain wet cake；Step S2, by Zr
(NO3)4·5H2O is dissolved in the hydrochloric acid solution of mass fraction 20%, and this hydrochloric acid solution is Zr (NO3)4·5H210 times of O weight；Step
Rapid S3, by wet cake stirring and dissolving in step S2 resulting solution, obtains mixed solution, evaporation mixed solution obtains white solid；Will
White solid and nano kaoline mixed grinding, the two weight ratio is 1:2.5, then in Muffle furnace, 600 DEG C of calcinings 4 are little
When；It is AlCl that glycerol adds weight3Add the 3% of weight；AlCl3With Zr (NO3)4·5H2O mol ratio is 1:1.5.
Embodiment 7：Effect example
The reduction of catalytic efficiency after respectively the conversion ratio (%) of testing example 1-6 and catalyst are recycled through 50 times
Percent value (%), result is as follows.
| Conversion ratio (%) | Catalytic efficiency reduces percentage rate (%) | |
| Embodiment 1 | 99.5 | 2.5 |
| Embodiment 6 | 90.4 | 39.5 |
Embodiment 2-5 measurement result is basically identical with embodiment 1, no longer enumerates one by one.
Result shows, the preparation technology high conversion rate that the present invention provides, solid catalyst can Reusability, and repeatedly apply mechanically
After 40 times, catalytic efficiency no significantly reduces.
The effect of above-described embodiment indicates that the essentiality content of the present invention, but does not limit the protection of the present invention with this
Scope.It will be understood by those within the art that, technical scheme can be modified or equivalent,
Essence without deviating from technical solution of the present invention and protection domain.
Claims (5)
1. one kind 4, the catalytic preparation process of 4'- dichloride methyl biphenyl it is characterised in that：Biphenyl, mass fraction are 27-37%
Hydrochloric acid and paraformaldehyde compare 1 according to weight:(3-4):(0.65-0.85) put in reactor, add solid catalyst, then
Add organic solvent, be warmed up to 50-80 DEG C, be passed through HCl gas, after reaction 10-20 hour, reacting liquid filtering gone out solid catalysis
Agent, liquid standing separates sour phase, and through washing, crystallizing, being filtrated to get crude product, crude product carries out recrystallization to organic faciess, obtains target
Product 4,4'- dichloride methyl biphenyl；Wherein, the preparation method of described solid catalyst comprises the steps：Step S1, spend from
Sub- water dissolution AlCl3, add glycerol, stir, ammonia adjusts pH value and obtains white precipitate, filter, wash, obtain wet cake；
Step S2, by Zr (NO3)4·5H2O is dissolved in the hydrochloric acid solution of mass fraction 15%-25%, and this hydrochloric acid solution is Zr (NO3)4·
5H28-12 times of O weight；Step S3, by wet cake stirring and dissolving in step S2 resulting solution, obtains mixed solution, evaporation is mixed
Close solution and obtain white solid；By white solid and modified Nano Kaolin mixed grinding, the two weight ratio is 1:2-3, so
In Muffle furnace, 500-700 DEG C of calcining 3-5 hour obtains final product described solid catalyst afterwards；It is AlCl that glycerol adds weight3Add weight
The 2-4% of amount；AlCl3With Zr (NO3)4·5H2O mol ratio is 1:0.5-2.5；
Described modified Nano Kaolin preparation method is：Taking nano kaoline 30-40 part to be scattered in 50-60 part mass fraction is 5-
In 15% disodium ethylene diamine tetra-acetic acid aqueous solution, stir 1-2 hour under the conditions of 40-50 DEG C, add 5-15 part nickel sulfate,
Stirring 20-30min, filters after cooling, is drying to obtain.
2. catalytic preparation process according to claim 1 it is characterised in that：Described modified Nano Kaolin preparation method
For：Taking 35 parts of nano kaoline to be scattered in 55 parts of mass fractions is in 10% disodium ethylene diamine tetra-acetic acid aqueous solution, in 45 DEG C
Under the conditions of stir 1.5 hours, add 10 parts of nickel sulfate, stir 25min, filter after cooling, be drying to obtain.
3. catalytic preparation process according to claim 1 it is characterised in that：Described organic solvent is hexamethylene, adds matter
Measure 3-7 times for biphenyl quality.
4. catalytic preparation process according to claim 1 it is characterised in that：The addition quality of described solid catalyst is connection
The 10-20% of benzene quality.
5. catalytic preparation process according to claim 1 it is characterised in that：The mole of the HCl gas being passed through is biphenyl
1.5-2.5 times of mole.
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| CN201610743114.4A CN106478362A (en) | 2016-08-26 | 2016-08-26 | A kind of catalytic preparation process of 4,4 ' dichloride methyl biphenyl |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362776A (en) * | 2020-04-25 | 2020-07-03 | 河北兰升生物科技有限公司 | Improved preparation method of 2, 5-disubstituted benzyl chloride |
| CN112573993A (en) * | 2020-11-20 | 2021-03-30 | 河北星宇化工有限公司 | Production process of 4, 4' -dichloromethyl biphenyl |
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| CN105503513A (en) * | 2015-12-08 | 2016-04-20 | 天津利安隆新材料股份有限公司 | Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid |
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2016
- 2016-08-26 CN CN201610743114.4A patent/CN106478362A/en not_active Withdrawn
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| CN105503513A (en) * | 2015-12-08 | 2016-04-20 | 天津利安隆新材料股份有限公司 | Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid |
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| 肖春妹 等: ""醋酸/甲醛缩合合成丙烯酸的研究"", 《河南科技学院学报》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362776A (en) * | 2020-04-25 | 2020-07-03 | 河北兰升生物科技有限公司 | Improved preparation method of 2, 5-disubstituted benzyl chloride |
| CN112573993A (en) * | 2020-11-20 | 2021-03-30 | 河北星宇化工有限公司 | Production process of 4, 4' -dichloromethyl biphenyl |
| CN112573993B (en) * | 2020-11-20 | 2023-03-14 | 河北星宇化工有限公司 | Production process of 4,4' -dichloromethyl biphenyl |
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