P.1 

OAR Box 1877 

Prepped by Keeia Richards 

Document Number: 

41) ll-B-38 

Docket Number: 

A-90-19 

Printed 12/2/2008 10:36:49 AM Sheet 41 of 46 
P.2 

MEMORANDU M 

TO: 

FROM: 

DATE: 

Process Vents Docket A-90-19 

Wanda Floyd 

December 1990 

A-90-19 

ll-B-38 

PJXOLI 

SEP 4I992 

EPAAIRDQCKFT 

SUBJECT: HON NESHAP: Industry Characteristics/Chlorophenols 

Attached is a product-process summary (PPS) for the production of 

Chlorophenols via Hydrolysis of Chlorobenzene category. This PPS was 

developed as part of the Industrial Profile project in support of the 

Hazardous Organic NESHAP (HON) regulatory effort. Information in this PPS is 

used as a basis for emissions and cost impact estimates for the HON program. 

Listed below are the key references used in developing the attached PPS. 

1989 Directory "f Chemical Producers USA. SRI International, California, 

p. 530. 

Genhartz, Wolfgang, ed. Ullmann's Encyclopedia of Industrial Chemistry, 

5th edition. VCH Publishers, Florida, 1985. p. 1-8. 

' '1 Pi >r n 

N. 

Doognenf is OOGIBI Item 

A-90-19 

ll-B-252 

cao.067 

chloro.phe 
P.3 

fl 

l(U Uft Preparer: l&Ld; M\ J 

Date: t-'+-io 

Reviewer: 

fmm^wmm^m 

ADMINISTRATIVE NOTES 

Hours spent on this PPS 1 

p.p Name C k io-r0?k e»oU v,Q L? Jr0l] ys */ cLlor* !>**??*,< 

Incomplete Items (parts of 

form you cannot complete) 

(ling # and description) Date Cleared initials 

^, elk*.* .f-i . H€'« * ^ " ^ * , 

Chemicals missing CAS numbers 

Plant with C1tv but no County (plant name, dty , statt) 

U**]o* Ukor,Kr.e, Uc. 8ran* rf 
P.4 

Chemical Nana 

PRODUCT-PROCESS SUMMARY (PPS) 

cttorofl e*ols 

Preparer: 

Date: 

Reviewer: 

PPS) 

Alterative gtpftgr 

i %S\61%oo 

v<j duMi 

<*X-X'X'X'X-X&%K%<^%<^ft;-X^'K-X^ 

o^cn^f 

wKv;-K<«w;« 

CHEHICAL SPECIFIC INFORMATION 

1.0 U.S. Production Ref # \lo . Pg I S Ref Year % S 

(Indicate the same reference Information for any answers below from a 

different reference) 

|^|§P^«:{fTO * H I (millions ofktOor millions of gallons 

w* 

1.7 Product Price 

i«k^-

W"* 

t\o 

TN(J 

AtcW 

AtcVtc 

ts-0 6a.V * U|V \ ^ 

>*> 

S/Ko or S/aallon 

1.8 Comments 
P.5 

\s*.L Al 

/ / L 

2.0 Che«1cal End-Use Ref # ° Pg # Ref Year 

Jiss Percent 

ay; coital 4^;cM ?*/ 
3.0 U.S. Producers Ref # 9 

., Pg # ., Ref Year in°{ 

BliniOn? of Kg J>r millions of gallons 

3.2 Naae, Location, and Capacity 

Process Used 

(use P-P I) 

)i<Xa^> i UlorJorieS, Tne tfronX^ , ^lf 

^fecolfj 0^1,'c S 7>iC Tr^ndil?.; / Q/f 

^?-9 \ 

9 -? \ 

Total Capacity \«\3 

•i*:=^?s«ii.-i!..'^,,i 
P.7 

PRODUCT-PROCESS SPECIFIC INFORMATION 

4.0 Potential Product-Processes (P-P) Ref I u 

., Pg * 

yo L-4 7 

3 

Commercially % Nat'l 

Naie. Viable (v/n, Caoadtv 

p.p j Cllorifle»0li y^g ^-j^rol-jSy *f cl, fo ft I <* 7 * * &- y 

p.p g Cl\aYofh^«li 5d £<//f**a/:** oS Cl7Jor0l,e.„pe.nf 

p.p 3 cl Uro pi e,ois ^'.* d.'g ?o f;fa f.'«« °f~ cl hr»«»/ I* e$ 

p.p 4 cllon>fle^„[ <; vie kjJ^oel eel fori xat'e* of. Pcl^H»ra4f>h^Js 

p.p 5 cl loroflt+Ac K'S kjdroKjUf^ °f cljorale^ ?i\,*S 

p.p 6 c-LUnfltmli K'« profile** *l*il<tt'«,»f cl/0r4^?*<e 

4.1 Documentation of P-Ps Excluded 

da j a 

A. 

P-P not 

Commercially Viable Reasons 

/N /^ ) I 

<U, ^fcy/ 

^e 
P.8 

Air Oxidation Reaction 

Oxidation Reaction 

Alkylation Reaction 

Carbonylation Reaction 

Halogenation Reaction 

Condensation Reaction 

Dehydrogenation Reaction 

Dehydrohalogenation Reaction 

Esterification Reaction 

Hydrogenation Reaction 

Hydrohalogenation Reaction 

Hydroformylation Reaction 

^yoYolysIs Reaction^ 

Nitration Reaction 

Oxyacetylation Reaction 

Oxyhalogenation Reaction 

Sulfonation Reaction 

Catalytic Reformation 

Hydrodimerization Reaction 

Ref I \i Pg # 

-'3L. % 

i 

I 

Generic Reaction 

4.4 Explain how you selected the reaction type In line 4.3. 

^ eja/W /- fit F-f"*-" 
P.9 

4.5 Written Description 

In the left margin, indicate references and page numbers throughout written 

description. 

ti2J>o[p5 of dloroh«?e,?j C w J, e C*n;tJ *J ^. «l^l'»? 

SSf~ £w, \ot cbmJL /" tU ^*?or pL$t 4 ZZo-^c 

pkotpUTel or &« S/l/ca 4 <S*°-Sr*°C. H^r*h^ ''*

 M**s

' 

s*J:*~ or pof*v;»»> ./ " I So-too*c 4 /- 5 *?« 

fie **^ (Shhrdph^ol v 
P.10 

5.0 Process Flow Diagram (attach at end of package) 

5.1 Flow Diagram Reference: Ref # 

5.2 Comments on Flow Diagram 

W cL&M 

., Pg # 

.r 

I 

I 

Component Tvnts 

Distillation Columns 

Absorbers 

Strippers 

Reactors 

Condensers 

Vaporizers 

Others 

Ref # 

1 

0 

a 

> 

o 

0 

0 

0 

2_ 

, Pg ' 
P.11 

6.0 Chemical Oata ^%^^-J-J) 

6.1 Balanced Chemical Reactions Ref I . pg # 

6.2 Chemical Tree Ref # , Pg # J 

-—r 

I 
6.4 Stoichiometry Ref I , Pg # 

C

t -5 

Show calculations and assumptions and then summarize 1n table on next 

page. 

Al 3 

))2. i" -T-... < 2 

/iff- 5 .+ 2 

^ 

c 

-_ tf. $x 

I 

I 

f 

P.12 
P.13 

6.4 StolchJometry Conversion Factors 

a) 

b) 

c) 

d) 

e) 

* v* vsss X9tw.r vXs-Xv^ •• •. A 

/.t f 

fcSjrsetarfor a-

^ SN*AAA>AWimvfrM4vSAVMANWSvMvSVA. A-S V.» 

^ W SSSS SVSSWrt*W. S V.VM W SV. SN .»SA S V N*rWM«C4NwC 

f) Conversion Factor Comments 

tu*^hc4 v°^ 
P.14 

6.4.1 Product 

y^C /, [o rafk t*,0 L(S) 

6.4.2 Raw Material(s) 

#1 

n 

#3 

#4 

#5 

6.4.3 

#1 

#2 

#3 

#4 

#5 

ci, lar»:l4» f*** 

^a fir 

Co-Products 

6.4.4 Bv-Products 

#1 .rV^^O 

#2 

#3 

#4 

#5 

§.4,5 

#1 

#2 

-

Intermediates 

\oprrf 

11J217S 

vnvto 

777 

£ 

I 

o-oi 
P.15 

7.0 Process Vent Emission Sources 

T.I Art thfr* process vent emlssldiisj 

7.1 Mr Oxidatiofl vettt e»lssions| _ 

Y 

v 

(Y/N) 

(Y/N) Ref # 

as C^Uh^Hff 

., Pg # 

7.3 Comments Ref I ., Pg # 

y (Y/N) Ref I ., Pg * 

7.5 Comments Ref I .. Pg # 
P.16 

A.SS t~~**j. 

H H H y _i _ (Y/N) Ref # , Pg # 

^ Col 

M .. S-" v» , 

7.9 Comments Ref I ., Pg # 

.3 

f 
0^ 

P.17 

Q<> <>L~A+/ 

8.0 Transfer Emission Sources 

8.1 * Art Prl^ts/G«-Pr^dycti 

8.2 What matertals are transferred? 

Ref # , Pg # 

X (Y/N) 

8.2.1 Product 

cXU roplz+^l 

8.2.2 Co-Products 

)j^M^ 

Z5ltf?°0 

8.3 Comments Ref I ., Pg # 
9.0 Storage Emission Sources 

9 M Ar« iatlriaTs stored! . > 

5.2 ^t materials «r* stored^ 

Ref I , Pg # 

(Y/N) 

P.18 

Nan* 

9.2.1 Product 

c. U*YofU**l 

9.2.2 Co-Products 

Storage Service 

Type 

-*5i*7.?0O 

\5f*ru***{Sjt 

I 

9.2.3 Raw Materials 

^*t*r-

\o?%l 5 for^i% J Jr*.„ rJSMJ 

-. i • 

9.4 Comments 
P.19 

$.<; C>U-JLJ 

10.0. Wastewater Emission Sources Ref # , Pg # 

10.1 1% %imm%%t pmeat? __il _ (Y/N) 

10.2 Describe wastewater 

Stream Equipment Component 

Number Producing Wastewater Comments on flow 

w X , 

#2 

#3 

10.3 Stream Composition Ref # , Pg # 

(provide only if readily available) 

Stream #1 j "jh Steam #2 

Organics Organics 

HAPs HAPs 

Water Water 

Other* " Other 
Stream #3 

Organics . 

HAPs 

Water 

Other 

P.20 

10.4 Comments Ref I ., Pg # 
P.21 

r-—i 

ST'^690C°.9

^^ 

198 9 DIRECTORY OF 

CHEMICAL PRODUCERS 

UNITED STATES OF AMERICA 

Information in this Directory is for the tola 

and private U M of sponsors of the 

Directory of Chemical Producers Program. 

RADIAN LIBRARY 

RESEARCH TRIANGLE PARK, NC 
P.22 

i ' ' 

333 RAVENSWOOD AVENUE 

MENLO PARK, CALIFORNIA 94025 

(415)859-3627 

FAX: (415)326-5512 

TWX: 910-373-2046 

TELEX: 334486 

Copyright © 1989 SRI International. Unauthorized use or reproduction of all or any part of this document is prohibited. Printed in U.S A 

««*• 
P.23 

* <V 1989 DIRECTORY OF CHEMICAL PRODUCERS 

UNITED STATES PRODUCTS 

1-Chk>ro-4-nitrobenzene (Cont'd) 

Monsanto Company 

Monsanto Chemical Company Sauget, Illinois 

Source: SRI International estimates as of January 1, 1989. 

TOTAL 

Annual Capacity 

(Millions of Pounds) 

85 

<M5 

Charles City, Iowa 

Great Meadows, New Jersey 

Orem, Utah 

Holley, New York 

2-Chloro-4-nitrobenzoic acid 

Solvay America, Inc. 

Salsbury Laboratories, Inc., 

subsidiary 

Salsbury Chemicals 

4-Chloro-3-flitrobenzoic acid 

AMAX Inc. 

Climax Metals Company, subsidiary 

Climax Molybdenum Company, 

subsidiary 

4-Chloro-2-nitrophenylurea 

Parish Chemical Company 

2-Chloro-S-nitropyridine 

Diaz Chemical Corporation 

2-Chloro-4-nttrotoluene (p-Nitro-o-chlorotoluene) 

E. I. du Pont de Nemours & Company, 

Inc 

Chemicals and Pigments 

Department Deepwater, New Jersey 

1-Chloro octadecane (See: n-Octadecyl chloride) 

1-Chloro-octane (See: n-Octyl chloride) 

1-Chloro-2-oxopropane (See: Chloroacetone) 

Chloroparaffins (See.- Chlorinated paraffins) 

Chloropentafluoroethane (F-115) 

E. I. du Pont de Nemours & Company, 

Inc 

Chemicals and Pigments 

Department 

Freon* Products Division Deepwater, New Jersey 

5-Chloro-2-pentanone 

Eastman Kodak Company 

Sterling Drug Inc, division 

Sterling Organics Division 

m-Chloroperoxybenzoic acid 

Aldrich Chemical Company, Inc. 

/3-Chlorophenetole 

R.SA Corporation 

m-Chlorophenol (3-Chlorophenol) 

Hexagon Laboratories, Incorporated 

Specialty Organics Inc. 

3-Chlorophanol (See: m-Chlorophenol) 

2-Chlorophenothiazine 

Chemical Dynamics Corporation 

SmithKline Beckman Corporation 

SmithKline Chemicals Division 

Rensselaer, New York 

Milwaukee, Wisconsin 

Ardsley, New York 

Bronx, New York 

Irwindale, California 

South Plamfield, New Jersey 

Conshohocken, Pennsylvania 

2-Chlorophenothiazine 10-carboxyiic chloride 

R.SA Corporation Ardsley, New York 

1-[4-Chloro-phenoxy]-3,3-dimethyl-1-{1,2,4-triazo-1-yf] 

butan-2-one (See: Triadimefon under Pesticides) 

3-[4-Chlorophenoxy]-1,2-propanediol carbamate (See: 

Chlorphenesin carbamate under Medicinal (Pharmaceutical) 

Chemicals) 

1-f4-Chlorophenyl (See.- Chlorcyclizine hydrochloride under 

Medicinal (Pharmaceutical) Chemicals) 

p-Chlorophenyl acetonitrile (p-Chlorobenzyl cyanide) 

Adron, Inc 

Orbis Products Corp. Newark, New Jersey 

2-Chloropheny.amine (See: o-Chloroaniline) 

3-Chlorophenylamine (See: m-Chloroaniline) 

4-Chlorophenylamine (See: p-Chloroaniline) 

4-Chloro-a-phenyr-o-cre«ol (See: o-Benzyr-p-chloropBenol 

under Pesticides) 

m-Chlorophenyl diethanolamine (2,2'-{[3-Chlorophenyl] 

imino] bisethanol) (N,N-0i-{2-hydroxyethyl] m-chloroaniline) 

Milliken & Co. 

Milliken Chemical Division Inman, South Carolina 

Quantum Chemical Corp. 

Emery Division Lock Haven, Pennsylvania 

p-Chlorophenyt-a-glyceryi ether carbamate (See: 

Chlorphenesin carbamate under Medicinal (Pharmaceutical) 

Chemicals) 

3-Chlorc-7-0-[2-phenylglycinamido}-3-cephem-4-

carboxylic acid (See: Cefaclor under Medicinal (Pharmaceutical) 

Chemicals) 

p-Chlorophenyl 2-hydroxyethyl sulfide 

Parish Chemical Company Orem, Utah 

2,2'-{[3-Chlorophenyl] imino] bisethanol (See: mChlorophenyl diethanolamine) 

p-Chlorophenyl magnesium chloride 

M&T Chemicals Inc Carrollton, Kentucky 

2-Chloro-4-phenylphenol (4-Phenyl-2-chlorophenol) 

Dow Chemical U.SA Midland, Michigan 

3-Chloro-1-phenylpropene (See: Cinnamyl chloride) 

4^hlorophenylseler>|r.yM>romide 

SynMet. Inc Memphis, Tennessee 

4-Chlorophenylselenenyl chloride 

SynMet, Inc

 J Memphis. Tennessee 

4-Chlorophenylselenol 

SynMet Inc Memphis. Tennessee 

1Kp^hlorophenyl8urfonyi}-3-propylurea (Sea 

Chlorpropamide under Medicinal (Pharmaceutical) Chemicaw 

530 SRI International 
Ullmann's 

Encyclopedia 

of Industrial 

Chemistry 

Volumes A1-A28: alphabetically arranged articles 

Volumes B1-B8: basic knowledge 

U 

E: 

oi 

C 

Fiftl 

Volun 

Abras 

Editorial Advisory Board 

Hans-Jiirgen Arpe 

Hoechst Aktiengesellschaft. 

Federal Republic of Germany 

Ernst Biekert 

Knoll AG, Federal Republic of Germany 

H. Edward Davis 

University of Minnesota. USA 

Heinz Gerrens 

BASF Aktiengesellschaft. 

Federal Republic of Germany 

Ralph H. Hirschmann 

Merck, Sharpe & Dohme, USA 

Tetsuji Kametani 

Hoshi University. Japan 

Akio Mitsutani 

Nippon Chetmech Consulting, Japan 

Charles Reece 

Imperial Chemical Industries. UK 

David P. Sheetz 

Dow Chemical. USA 

Howard E. Simmons 

E. I. Du Pont de Nemours. USA 

Eberhard Weise 

Bayer AG, Federal Republic of Germany 

Rudolf Wirtz 

Hoechst Aktiengesellschaft, J 

Federal Republic of German^-

Hans-Rudolf Wuthricrr' -

Metallgesellschaft AG. Federaj, Republic 

of Germany , j 

Execu 

Senioi 

Editoi 

James 

MOMM 
Vol. A1 

Numerical data, descriptions of methods or equipment, and other information presented in this book 

have been carefully checked for accuracy. Nevertheless, authors and publishers do not assume any 

liability for misprints, faulty statements, or other kinds of errors. Persons intending to handle 

chemicals or to work according to information derived from this hook are advised to consult the 

original sources as well as relevant regulations in order to avoid possible hazards. Prefac 

Production Director: Maximilian Montkowski 

Production Manager: Myriam Nothacker 

Library of Congress Card No. 84-25-829 

Deutsche Bibliothek. Cataloguing-in-Publication Data: 

Ullmann's Encyclopedia of Industrial Chemistry / ed. Wolfgang Gerhartz ... [ed. advisory board 

Hans-Jiirgen Arpe ...]. - Weinheim; Deerfield Beach, Florida; Basel: VCH Verlagsgesellschaft 

Bis 4. Aufl. u. d. T.: Ullmanns Enzyklopadie der Technischen Chemie 

NE: Gerhartz, Wolfgang [Hrsg.]; Encyclopedia of Industrial Chemistry 

Vol. A. Alphabetically arranged articles. 

1. Abrasives to Aluminum Oxide. - 5th. completely rev. ed. - 1985. 

ISBN 3-527-20101-7 (Weinheim) 

ISBN 0-89573-151-7 (Deerfield Beach. Florida) 

© VCH Verlagsgesellschaft mbH, D-6940 Weinheim (Federal Republic of Germany), 1985. 

Distribution: VCH Verlagsgesellschaft, P.O. Box 1260/1280. D-6940 Weinheim (Federal Republic of Germany) 

USA and Canada: VCH Publishers. 303 N.W. 12th Avenue. Deerfield Beach, FL 33441-1705 (USA} 

All rights reserved (including those of translation into other languages). No part df this book may be 

reproduced in any form - by photoprint, microfilm, or any other means - nor transmitted or translated 

into a machine language without written permission from the publishers. 

Registered names, trademarks, etc. used in this book and not specifically marked asiuch are not to be 

considered unprotected. 

Cover design: Wolfgang Schmidt 

Composition, printing, and bookbinding: Graphischer Betrieb Konrad Triltsch, D-8700 Wurzburg 

Printed in the Federal Republic of Germany 

About t 

Fritz L'llma: 

saw the nee 

furnish recir. 

cal industry 

ing famous 

know how i 

Enzyklopddi 

born. 

During i 

Encyclopedi 

intoaconcis 

source of ir. 

and practic; 

Now. in its 

evident. 

Themos 

the Encyclot 

than in the 

though ace 

change, it o: 

t:rship. tacili 

authors, aru 

The subj 

clopeuia ha? 

the progress 

New topics !• 

disciplines 

tronics. phu 

Added emp 

broad conce 

industrial ir. 

high cost a: 

'.trials and e 

tect the env 

:uture gene 

•.'nd proc 

HI 
P.26 

' ' , i 

Vol. A 7 Chlorophenols 

Chlorophenols .c 

.~.CY"'~ 

FRANCOIS MULLER, Rhone-Poulenc, Le Pont-de-Claix, France (Chaps. 1-9) Y ' 

LILIANE CAILLARD, Rhone-Poulenc, Courbevoie, France (Chap. 10) 

B H 1 '• 

^^^^^^^^^^^^^H: 

1. Physical Properties 1 

2. Chemical Properties 1 

2.1. Reactions of the Hydroxyl Group 1 

2.2. Electrophilic Substitution of the Ring ... . 2 

2.3. Nucleophilic Substitution of the Ring 2 

2.4. Oxidation Reactions 3 

3. Production 3 

3.1. Mono-, Di-, and Trichlorophenols with 

no Chlorine in a Meta Position; Tetrachlorophenols; and Pentachlorophenol ... . 3 

3.2. Mono-, Di-, and Trichlorophenols with 

Chlorine in a Meta Position 4 

In chlorophenols the aromatic ring of phenol 

is substituted with one to five chlorine atoms. 

LAURENT discovered this group of compounds 

when he chlorinated coal tar in 1836 [1], [2]. 

Chlorophenols are industrially important because of their broad spectrum of antimicrobial 

properties and their uses as fungicides, herbicides, insecticides, ovicides, and algicides. A mixture of tctrachlorophenols and pentachlorophenol. either as such or as salts or esters, finds 

widespread use as a preservative for wood, glue, 

paint, vegetable fibers, and leather. In addition, 

chlorophenols are widely used as intermediates 

in chemical syntheses. 

1. Physical Properties 

Important characteristics and physical properties of chlorophenols are shown in Tables 1 

and 2. With the exception of 2-chlorophenol, 

these compounds are solid at ambient temperature; they all have strong characteristic odors. 

Several of them sublime readily. They can be 

steam-distilled. The chlorophenols are only 

slightly soluble in water, but highly soluble in 

alcohols. They impart a strongly disagreeable 

taste to drinking water. 

4. Analysis 4 

5. Quality Specifications 5 

6. Economic Aspects 5 

7. Uses 5 

8. Storage and Transportation 6 

9. Environmental Considerations 6 

9.1. Toxicity to Fauna and Flora 6 

9.2. Persistence in the Environment 7 

10. Toxicology 7 

11. References 8 

2. Chemical Properties 

Chlorophenols are versatile intermediates in 

chemical syntheses because both the hydroxyl 

group and the aromatic ring can react by both 

electrophilic and nucleophilic substitution. They 

are readily oxidized. 

2.1. Reactions of the Hydroxyl Group 

Chlorophenols are more acidic than phenol and readily form salts with alkali and 

alkaline-earth hydroxides or carbonates or with 

amines. These salts are stable and soluble in 

water. 

Chlorophenols readily form esters of both 

organic and mineral acids [3]-[5]. Esters such as 

chlorophenyl phosphates, carbamates [6], [7], 

chloroformates [8], carbonates, and laurates 

are widely used. Pentachlorophenyl 2-ethylhexanoate is used as a textile preservative. 

Chlorophenols are also readilwp-alkylated, 

and ethers derived from aliphatic, aromatic, and 

heterocyclic reagents comprise a broad class of 

industrial products [9], [10]. One'of the most 

widely known is 2,4-dichloropheno'jcyacetic acid 
P.27 

Chlorophenols Vol. A 7 Vol. A7 

Table 1. Characteristics of the chlorophenols 

Chlorophenol 

2-Chlorophenol [95-57-8] 

3-Chlorophcnol [108-43-0] 

4-Chlorophenol [106-48-9] 

2.3-Dichiorophenol [576-24-9] 

2,4-Dichlorophenol [120-83-2] 

2,5-Dichlorophenol [583-78-8] 

2.6-Dichlorophenol [87-65-0] 

3,4-Dichlorophenol [95-77-2] 

3.5-Dichlorophenol [591-35-5] 

2.3,5-Trichlorophenol [933-78-8] 

2,4.5-Trichlorophenol [95-95-4] 

2,4,6-Trichlorophenol [88-06-2] 

2,3,4-Trichlorophenol [15950-66-0] 

3,4.5-Trichlorophenol [609-19-8] 

2.3.6-Trichlorophenol [933-75-5] 

2,3.5.6-Telrachlorophenol [935-95-5] 

2,3,4,6-Tetrachlorophenol[J«-90-2] 

2,3,4,5-Tetrachlorophenol[490/-5/-i] 

Pentachlorophenol [87-86-5] 

Formula 

C6H,CIO 

C6HaC10 

C6H3C10 

C6H4C120 

C8H4C120 

C6H4C120 

C6H4CI20 

C6H4CI20 

C6H4CI20 

C6H3C1,0 

C6H3C130 

C6H3C130 

C6H3C130 

C.HjCljO 

C.HJCIJ O 

C6H2CI40 

C6H2C140 

C6H2C140 

C6HC1,0 

M, 

128.56 

128.56 

128.56 

163.00 

163.00 

163.00 

163.00 

163.00 

163.00 

197.45 

197.45 

197.45 

197.45 

197.45 

197.45 

231.89 

231.89 

231.89 

266.34 

mp, °C 

8.7 

32.8 

42.8 

58 

45 

59 

66 

65 

68 

62 

68 

68 

83.5 

101 

101 

115 

69-70 

116-117 

190 

bp,°C 

174.5 

216 

217 

206 

210 

210 

220 

253 

233 

248-249 

245-246 

246 

subl. 

275 

272 

subl. 

164 (3 kPa) 

subl. 

309-310 

P*. 

8.52 

8.97 

9.37 

7.71 

7.90 

7.51 

6.78 

8.62 

8.25 

6.72 

5.99 

6.97 

7.55 

5.80 

5.03 

5.22 

5.64 

4.74 

Table 2. Physical properties of the most important chlorophenols 

Property 

bp,°C 

at 0.1333 kPa 

at 1.333 kPa 

at 5.333 kPa 

at L3.33 kPa 

at 53.33 kPa 

Specific heat at 20 

Heat of formation 

Viscosity at 50 °C. 

Solubility in water 

Flash point (closec 

°C, J mol"1

 K~' 

at 50 °C, kJ/mol 

mPa 

at 20 

cup) 

s 

°C g/L 

>C 

2-Chlorophenol 

12 

51 

82 

106 

150 

172 

185 

2 

28.5 

121 

4-Chlorophenol 

50 

92 

125 

150 

190 

177 

198.9 

5 

27.1 

84 

2,4-Dichlorophenol 

53 

93 

123 

146 

187 

190 

2.65 

4.5 

113 

2,6-Dichlorophenol 

59.5 

101 

131.6 

154.6 

197.7 

2,4,6-Trichldrophenol 

76.5 

120.2 

152.2 

177.8 

222.5 

0.8 

Pentachlorophenol 

132 

178 

295 

0.014 

[95-75-7] (2,4-D), which is still used as a selective herbicide for broadleaf plants [11]-[13] 

(->• Chlorophenoxyalkanoic Acids). 

2.2. Electrophilic Substitution 

of the Aromatic Ring 

Electrophilic substitution is favored by the 

presence of chlorine atoms on the aromatic nucleus; thus, most chlorophenols partake in the 

standard reactions, such as alkylation [14], acylation, nitration, sulfonation, halogenation, [15], 

[16], carboxylation, and condensation with aldehydes, e.g., formaldehyde, chloral, glyoxylic acid 

[17]-[19]. 

2.3. Nucleophilic Substitution 

of the Aromatic Ring 

Nucleophilic substitution for one or more of 

the chlorine atoms, although disfavored by the 

presence of the other chlorine atoms, is nevertheless used widely. 

The hydrolyses of 2-chlorophenol and 4-

chlorophenol were used at one time to obtain pyrocatechol [120-80-9] and hydroquinone 

[123-31-9], respectively. The ammonoiysjs of 

2-chlorophenol or 4-chlorophenol produces 2-

aminophenol or 4-aminophenol, rejpechvely. 

This type of reaction is used primarily to prepare 

various substituted diphenyl ethers, which serve 

as efficient herbicides [20] - [22]. 

Chlorophenols can be c 

chlorinated alicyclic ketones 

rophenol" [599-52-0] by rea 

aqueous acetic acid. "Hex: 

pesticidal properties and is h 

nil [2435-53-2] in the presen 

lyst such as sulfuric acid. 

2

U 

ci-J^c i 

ci-^xYci 

ci ci 

'Hezschloropheaal* 

2.4. Oxidation Reactiot 

Like other phenols, ch 

oxidized; air oxidation for 

whereas oxidation with hyd 

to the corresponding ch 

Oxidation by a peroxide s 

acid in benzene at 80 °C yii 

(85% yield) [23]: 

OH OH 

6"- 6C 

3. Production 

There are two types ot 

those with one to three chic 

in a meta (3 or 5) position 

those which have four or 

and (2) those with one to t 

at least one being in a mt. 

to OH. 

3.1. Mono-, Di-, and Ti 

with no Chlorine in a IV 

Tetrachlorophenols; 

and Pentachlorophenol 

The mono-, di-, and trie 

have no chlorine atom in th 

tion relative to OH are 2-chl 

phenol, 2,4-dichlorophenol. 
A 7 

p* . 

8.52 

8.97 

9.37 

7.71 

7.90 

7.51 

6.78 

8.62 

8.25 

6.72 

5.99 

6.97 

7.55 

5.80 

5.03 

5.22 

5.64 

4.74 

hcnol 

>re of •y the 

lever- id 4- > ob

-

inone 

;is of 

:es 2-

ively. 

epare 

serve 

P.28 

li 

i 

Vol. A 7 

Chlorophenols can be converted into poly-

chlorinated alicyclic ketones such as "hexachlo-

rophenol" [599-52-0] by reaction of chlorine in 

aqueous acetic acid. "Hexachlorophenol" has 

pesticidal properties and is hydrolyzed to chlora-

nil [2435-53-2] in the presence of an acidic cata-

lyst such as sulfuric acid. 

H-,0 

ci^X/a II

 + 

ci'Yc^ci a ci 

'Hexachlorophenol 

C1,JL,C1 I f +

2 HCI 

ci'YY

v

c i 

0 

2.4. Oxidation Reactions 

Like other phenols, chlorophenols can be 

oxidized; air oxidation forms chloroquinones, 

whereas oxidation with hydrogen peroxide leads 

to the corresponding chlorinated diphenol. 

Oxidation by a peroxide such as perpropionic 

acid in benzene at 80 °C yields chlorodiphenols 

(85% yield) [23]: OH 

(S 

OH 6f 

OH 

Cl 

OH 

3. Production 

There are two types of chlorophenols: (1) 

those with one to three chlorine atoms but none 

in a meta (3 or 5) position relative to OH and 

those which have four or five chlorine atoms, 

and (2) those with one to three chlorine atoms, 

at least one being in a meta position relative 

to OH. 

3.1. Mono-, Di-, and Trichlorophenols 

with no Chlorine in a Meta Position; 

Tetrachlorophenols; 

and Pentachlorophenol 

The mono-, di-, and trichlorophenols which 

have no chlorine atom in the meta (3 or 5) posi-

tion relative to OH are 2-chlorophenol, 4-chloro-

phenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 

Chlorophenols 3 

and 2,4,6-trichlorophenol. The tetrachlorophe-

nols and pentachlorophenol are also included 

with this type. These compounds are obtained by 

the direct chlorination of phenol. 

The chlorination of melted phenol [108-95-2] 

using chlorine gas [7782-50-5] yields a mixture of 

ortho and para monochlorophenols with an o/p 

ratio of ca. 0.54 (35/65), which is scarcely de-

pendent on temperature. The distribution be-

tween the two isomers depends especially on the 

nature of the chlorination reagent and the char-

acteristics of the reaction medium. The forma-

tion of 2-chlorophenol is favored by an aprotic 

nonpolar solvent medium, such as hexane, car-

bon tetrachloride, or dichloroethane. The o/p 

ratio is also higher for reactions with a low con-

centration of phenol and a high temperature 

[24]. The chlorination of a 5 % solution of phe-

nol in perchloroethylene at 110°C in the pres-

ence of 0.01 wt% diisopropylamine [108-18-9] 

gives a very high ojp ratio, ca. 15 [25]. Chlorina-

tions using aqueous sodium hypochlorite 

[7681-52-9] at pH 10, tert-b\xty\ hypochlorite 

[507-40-4] and alkali phenolates dispersed in an 

anhydrous medium [26], or chlorine in acetic 

acid in the presence of acetic anhydride 

[108-24-7] also favor the formation of 2-chloro-

phenol [27]. 

The formation of 4-chlorophenol is favored 

by chlorination in a polar medium, such as ace-

tonitrile, nitrobenzene, or ether [28]—[31]. Sub-

stitution in the para position is also strongly favored by the use of sulfuryl chloride [7791-25-5] as a chlorinating agent {ojp = 0.35) [28], [31]. 

Certain organic sulfides, e.g., diphenyl sulfide 

[139-66-2], activate chlorination and favor sub-

stitution at the para position [32]. Chlorination 

using copper(II) chloride in aqueous hydrochlo-

ric acid in the presence of oxygen leads to 

4-chlorophenol (almost 100%) [33]. 

Mono-, di-, and trichlorophenols are made 

industrially by chlorination of phenol with 

chlorine gas in a melt in cast-iron reactors. The 

isomer distribution in the product may be ad-

justed to market demands by the chlorination 

level and by recycling various intermediates. The 

yield, based on chlorine and phenol, is greater 

than 95%. 

Tetrachlorophenols and pentachlorophenol 

are produced batchwise in niclrfl reactors by 

the chlorination of less halogenated chloro-

phenols in the presence of aluminum trichloride 

[7446-70-0] or iron trichloride [7105-08-0]. 
I I , < 

Chlorophenols 

OH OH 

Vol. A 7 

OH X 

6

X

' 

OH OH y a CU a 

3.2. Mono-, Di-, and Trichlorophenols 

with Chlorine in a Meta Position 

The mono-, di-, or trihalogenated phenols 

having at least one chlorine atom in a meta position are 3-chlorophenol, 2,3-dichlorophenol, 

2,5-dichlorophenol, 3,4-dichIorophenol, 3,5-dichlorophenol, 2,3,4-trichlorophenol, 3,4,5-trichlorophenol, and 2,3,6-trichlorophenol. 

These compounds cannot be obtained by the 

chlorination of phenol, but must be made by 

other types of reactions, such as hydrolysis, sulfonation, hydrodechlorination, hydroxylation, 

and alkylation. 

Hydrolysis of chlorobenzenes can be carried 

out in alkaline aqueous media, with or without 

the presence of copper salts [34]. It can be done 

in the vapor phase at 250-400 °C on phosphates 

[35] or on silica at 500-550 °C [36]. Hydrolysis is 

most frequently carried out in the presence of 

methanolic sodium or potassium at 150-200°C 

and 1.0-3.0 MPa [37], [38]. 

Sulfonation-Desulfonation. Sulfonation of 

chlorobenzenes followed by the desulfonation of 

chlorobenzenesulfonic acids can be used to produce numerous chlorophenols [39]-[44]. The 

chlorobenzenes are sulfonated by using 15-20% 

oleum at 60-80 °C. The subsequent desulfonation is usually carried out by using 15-25% 

aqueous sodium hydroxide solution at 180— 

220°C and 1.5-3.0 MPa. 

SandmeycV Reaction. w-Chlorophcnols can 

also be made by diazotization ofthe corresponding chloroanilines that have been obtained either 

by nitration of chlorobenzenes followed by hydrogenation or by chlorination of nitrobenzenes 

[42]. 

irhere ib => relative rate constant 

kz = 1090; * 4 = 1910; * 2 4 = 124; k'Zi = 81 

*2.» -

 i6

- *2.4.e " °-7- *2.4.6 " °- 9 

Hydrodechlorination. Hydrodechlorination 

of polychlorophenols produces 3-chlorophcnols. 

This reaction has long been carried out either in 

the vapor phase at 300-350°C on an alumina 

catalyst [45] or in the liquid phase at 150-250 °C 

and 15.0-20.0 MPa, usually in the presence of 

sulfur [46], [47]. More recently, catalytic hydrodechlorination of polychlorophenols in organic 

or aqueous media with a palladium catalyst was 

used to obtain 3-chlorophenol and 3,5-dichlorophenol [48]. Hydrodechlorination of polychlorophenols with hydriodic acid in an aqueous or 

organic medium has also been reported [49]. 

Hydroxylation. Hydroxylation of chlorobenzenes gives a mixture of 55 wt % 4-chlorophenol, 

30-35 wt% 2-chlorophenol, and 15wt% 3-

chlorophenol [50]. 

Hock Phenol Synthesis. The propylene alkylation of a chlorobenzene followed by oxidation 

and decomposition of the hydroperoxide in an 

acid medium produces the corresponding chlorophenol [46], [51]. 

The physical properties of the principal commercial chlorophenols are given in Table 2. 

4. Analysis 

The acidity of the phenol function in chlorophenols increases with increasing chlorination of 

the benzene ring. Potentiometric analysis with 

either soda in an aqueous medium or an amine in 

an organic medium is, ihcrcfore, suitable. Good 

sensitivity is obtained by using cychjhexylamine 

in ethylene glycol monoethyl ether absolvent 

[53], [54]. 

Chlorophenols are difficult to -separate by 

gas chromatography because of their4iigh acidiP.29 

Vol. A7 

ty. However, the light hi 

rated by using an acidic s> 

column. The heavy home 

only after the phenol fu 

means of methylation, ace 

phthalation. Traces of chl. 

termined as their trifluorc 

by gas chromatography 

detection (limit of detect: 

[54]. 

All phenols are co 

reverse-phase HPLC on i 

with C18 species. Grafts o 

enable separations based i 

nation (the retention time 

UV (280 nm) detection is 

rometric detection is 10( 

[55]-[58]. 

IR spectrometry can c 

different isomers, which 

1600-400cm"' [59]. Pre 

try can identify most ot 

phenols by the chemical si 

their aromatic protons. F 

be identified after the pi 

complexed with hexameth 

[680-31-9]. Carbon-13 rthan proton NMR, but it 

useful information [60]. 

The individual chloro 

fied and determined wit 

means of gas chromat. 

chemical ionization ma: 

chlorophenols are first co 

fluorobenzyl ether or pe: 

derivatives. The analysis 

these species because of th 

tivity [61]. 

Thermal or chemical • 

phenols can produce sub 

rious to the environment, 

benzoparadioxins, pol 

and polychlorophenoxyr 

These substances can be 

with UV detector at a se; 

[50], [52]. Determination: 

quire that the sample be p 

major portion of the chen 

sample is first extracted 

dium with hexane and the 

mina liquid chromatogra 

The chosen compoun 

ed into homologous groui 

mination is made by using 
P.30 

)l. A7 Vol. A 7 Chlorophenols 

ation 

.'nols. 

ier in 

:mina 50 °C ce of 

ydroganic t was 

loro-

loro- is or 

>1. 

ilky-

ition n an 

:hlo-

ty. However, the light homologs can be sepa-

rated by using an acidic solid support in a glass 

column. The heavy homologs can be separated 

only after the phenol function is blocked by 

means of methylation, acetylation, silylation, or 

phthalation. Traces of chlorophenols may be de-

termined as their trifluoroacetylated derivatives 

by gas chromatography with electron capture 

detection (limit of detection ca. 20 mg/L) [52], 

[54]. 

All phenols are correctly separated by 

reverse-phase HPLC on a silica column grafted 

with C,

8 species

. Grafts of the propylamino type 

enable separations based on the degree of chlori-

nation (the retention time depends on the pKJ. 

UV (280 nm) detection is normally used; ampe-

rometric detection is 100 times more sensitive 

[55]-[58], IR spectrometry can distinguis

h between the 

different isomers, which absorb in the region 

1600-400 cm"

1

 [59]. Proton NMR spectrome-

try can identify most of the different chloro-

phenols by the chemical shift and the coupling of 

their aromatic protons. Pentachlorophenol can 

be identified after the phenol group has been 

complexed with hexamethylphosphoric triamide 

[680-31-9]. Carbon-13 NMR is less sensitive 

than proton NMR, but it can provide even more 

useful information [60]. 

The individual chlorophenols can be identi-

fied and determined with great sensitivity by 

means of gas chromatography followed by 

chemical ionization mass spectrometry. The 

chlorophenols are first converted to their penta-

fluorobenzyl ether or pentafluorobenzoic ester 

derivatives. The analysis is then carried out on 

these species because of their higher electronega-

tivity [61]. 

Thermal or chemical degradation of chloro-

phenols can produce substances that are delete-

rious to the environment. Certain polychlorodi-

benzoparadioxins, polychlorodibenzofurans, 

and polychlorophenoxyphenols are examples. 

These substances can be determined by HPLC 

with UV detector at a sensitivity of ca. 1 mg/kg 

[50], [52]. Determinations at the |xg/kg level re-

quire that the sample be pretreated to remove the 

major portion of the chemical interferences. The 

sample is first extracted from an alkaline me-

dium with hexane and then separated on an alu-

mina liquid chromatography column. 

The chosen compounds can then be collect-

ed into homologous groups [62]. The final deter-

mination is made by using GC with electron cap-

ture detection or by combined gas chromatogra-

phy and mass spectrometry. The limit of detec-

tion for 2,3,7,8-tetrachlorodibenzo-/wra-dioxin 

[1746-01-6] (TCDD) is less than <1 ng/kg [52]. 

5. Quality Specifications 

The minimum assay for commercial chloro-

phenols is 98.5 wt%. More often than not, it is 

>99wt% and at times even 99.5 wt%. The 

APHA color number is always < 100. The prin-

cipal impurities are other isomers of the chloro-

phenol or chlorophenols with more or fewer 

chlorine atoms. In the majority of cases, the 

2,4,5-trichlorophenol content is < 20 mg/kg. 

The absence of chlorobenzoparadioxins, chloro-

benzofuran, and most often chlorobenzenes 

should be noted. 

Polychlorophenoxyphenols are the major 

impurity (up to several percent) in the heavy 

chlorophenols, which are marketed as mixtures 

of tetrachlorophenols and pentachlorophenol. 

Trace quantities of chlorobenzoparadioxins and 

chlorobenzofuran are also found. The highly 

toxic compound 2,3,7,8-tetrachlorodibenzo-

para-dioxin has never been detected in products 

made by chlorination [52]. The sodium salts of 

the heavy chlorophenols contain the same impu-

rities as the parent compounds. 

6. Economic Aspects 

The world market, excluding the Comecon 

countries and China, is fairly stable and is ca. 

100 kt/a. 

The production of heavy chlorophenols is 

25-30 kt/a. Of this 16-20 kt/a is produced in 

the United States (Vulcan, Reichhold), 8-

10 kt/a in Western Europe (Rhone-Poulenc, 

Dynamit Nobel), and 2 kt/a elsewhere in the 

West. 

Production of light chlorophenols is ca. 

60 kt/a. Of this, 18-20 kt/a is made in the United 

States (Dow) and 30 kt/a in Western Europe 

(Rhone-Poulenc, BASF, Coalite, Bayer, Chemie 

Linz, Esbjerg, KVK). 

7. Uses 

<Y 

Chlorophenols are used as agricultural chem-

icals, pharmaceuticals, biocides, and dyes. 
6 Chlorophenols 

Agricultural Chemicals. The preparation of 

agricultural chemicals consumes 80-90%) of 

chlorophenol production. The annual consumption of the herbicides 2,4-dichlorophenoxyacetic 

acid (2,4-D) and 2,4-dichlorophenoxy-4-butyric 

acid is 30-40 kt. Hoelon (Hoechst), Modown 

(Mobil), Ronstar (Rhone-Poulenc), and TOK E25 (Rohm and Haas) are among the major herbicides. Curacron (Ciba Geigy) exemplifies the insecticides made from chlorophenols. Among the 

fungicides are Bayleton (Bayer), MO (Mitsui 

Toatsu Chemicals), and Procloraz or Sportak 

(Boots). 

Pharmaceuticals. Pharmaceuticals derived 

from chlorophenols include clofibrate, ethyl 

2-(4-chlorophenoxy)-2-methylpropionate (ICI), 

used in the treatment for high serum cholesterol, 

and Mervan or Aldofene, an antiinflammatory 

and analgesic drug (Continental Pharma). 

Biocides. Biocides that are based on chlorophenols include the molluscicide Bayluscide 

(Bayer) and the bactericide Santophen or Chlorophen (Monsanto). Pentachlorophenol is also 

used to make wood and cellulose preservatives, 

esters for the textile and leather industries, 

paints, varnishes, and organic adhesives. 

The sodium salt of pentachlorophenol is an 

active, water-soluble material. It is used as a preservative for such organic materials as freshly 

sawn wood (against blue rot), paints, adhesives, 

textiles, leather, and furs. 

Dyes. Chlorophenols are used in the synthesis of anthraquinone dyes (-* Anthraquinone 

Dyes and Intermediates). Quinizarin, 1,4-dihydroxy-9,10-anthracenedione [81-64-1], is the 

most important example. 

8. Storage and Transportation 

The production, storage, transportation, and 

use of chlorophenols are subject to regulations 

and stipulations that depend on the products and 

on the countries concerned. Within the EEC, directive 67/548 governs classification, packing, 

and labeling; directive "131" 76/464 covers discharges from production plants into aquatic media; directives 77/728 and 78/631 regulate the relevant paints and pesticides, respectively. 

Vol. A 7 

Transportation of chlorophenols is governed 

by international regulations such as IMDG 

Code (sea), IATA-DGR (air), RID (rail), and 

ADR (road). 

9. Environmental Considerations 

Chlorophenols are hazardous to the environment and have been the subject of numerous ecological surveys of fauna and flora in aquatic, terrestrial, and aerial environments [63]. 

9.1. Toxicity to Fauna and Flora 

Microorganisms. All chlorophenols possess 

bactericidal activities that increase with the degree of chlorination and attain a maximum for 

the trichlorophenols. Their metabolic effects 

include enzyme inhibitions of oxidative phosphorylation and the synthesis of adenosine triphosphate. Chlorophenols are highly toxic to algae. Trichlorophenols are at least 100 times more 

toxic than dichlorophenols, and pentachlorophenol is used as an algicide. 

Plants. Chlorophenols possess a phytotoxicity that increases with the degree of chlorination. 

The absorption of chlorophenols by plants depends on the solubility of the product and pH of 

the environment. Terrestrial and aquatic plants 

can in certain cases absorb, transform, and eliminate chlorophenols without harm, but most often these plants are very sensitive to the phytotoxicity of chlorophenols. 

Aquatic Organisms. Fish and other aquatic 

organisms absorb chlorophenols through their 

gills, gastrointestinal tract, or skin. Measurements over 2-4 d show that acute toxicity for 

invertebrates, Crustacea, and freshwater and seawater fish increases with the level of chlorination. For mono-, di-, and trichlorophenols, the 

2-4 d LCJ0 is 0.6-10.3 mg/L, depending on the 

species. For pentachlorophenol, it is 0.03-

0.6 mg/L, except for certain resistant invertebrates that can survive concentrations *of 5-

10 mg/L. • " 

Chlorophenols also have a long-^rrn^toxic 

effect at low concentrations. 2,4-Dichlqrophenol 

and 2,4,6-trichlorophenol at concentrations of 

6.2-10.3 mg/L affect the fertilization of sea urP.31 

Vol. A 7 

chin eggs, and pentachloroi 

and hepatic lesions in fish 

mends that the maximum a 

phenol concentration in sur 

ceed 0.055 mg/L. For 2,4-c 

2-chlorophenol, the EPA set 

centrations at 2.020 and 4.38 

[64]. This limitation, based c 

thened by the fact that chic 

mulate to only a small extei 

9.2. Persistence in the I 

Aquatic Environment. Ch 

present in the aquatic en' 

forms. They may be dissol 

plexed form, adsorbed on s 

or biological materials or b 

carried in biological tissues 

by biodegradation, photodc 

lization to the atmosphere, 

Biodegradation is the [ 

which chlorophenols are rt 

induced because the antimi 

these products require that 

Biodegradation is rapid wh< 

ganisms are already preser. 

phenol is more difficult.to 

other chlorophenols. 

Chlorophenols photode 

posed to UV light, such as s 

surface. 

Volatilization transfers 

from the water to the air bu 

affect it. The adsorption o 

suspended or benthic mater 

in the amount of chlorophe 

chlorophenols are fixed to 

but pentachlorophenol adsc 

certain types of particles \ 

suitable. 

Terrestrial Environment. 

chlorophenols in the soil 

adsorption-desorption cha: 

adsorption of pentachlorop 

ied in depth. It attaches ve 

and is not easily washed au 

Atmosphere. The presen 

in the atmosphere has bee 

detection of minute quanti 

phenol in rainwater and sn> 
/Ol. A 7 Vol. A7 Chlorophenols 

overned 

IMDG 

iii), and 

IS 

;nvironousecoatic, tery 

| 

| 

I 

:

: 

< 

possess 

the denum for 

ell eels 

c phos-

•sine iridic to alles more 

ichloro- 1 

totoxic-

"ination. [\ 

ants de- ;j 

id pH of ?j 

c plants *| 

idelimi- ;i 

most of- i] 

e phyto- ;) 

: • ) 

aquatic 'j 

gh their 

'leasureicity for 

and seahlorinalols, the 

g on the 

s 0.03- •; 

inverte- , 

s of 5- :"j 

chin eggs, and pentachlorophenol causes renal 

and hepatic lesions in fish. The EPA recommends that the maximum average pentachlorophenol concentration in surface waters not exceed 0.055 mg/L. For 2,4-dichlorophenol and 

2-chlorophenol, the EPA set the maximum concentrations at 2.020 and 4.380 mg/L, respectively 

[64]. This limitation, based on toxicity, is strengthened by the fact that chlorophenols bioaccumulate to only a small extent [65], [66]. 

9.2. Persistence in the Environment 

Aquatic Environment. Chlorophenols may be 

present in the aquatic environment in many 

forms. They may be dissolved in free or complexed form, adsorbed on suspended inert solid 

or biological materials or benthic sediments, or 

carried in biological tissues. They are removed 

by biodcgradalion. photodccomposilion, volatilization to the atmosphere, and adsorption. 

Biodegradation is the principal means by 

which chlorophenols are removed. It must be 

induced because the antimicrobial activities of 

these products require that the bacteria adapt. 

Biodegradation is rapid when adapted microorganisms are already present, but pentachlorophenol is more difficult to biodegrade than the 

other chlorophenols. 

Chlorophenols photodecompose when exposed to UV light, such as sunlight on the water 

surface. 

Volatilization transfers the chlorophenol 

from the water to the air but does not otherwise 

affect it. The adsorption of chlorophenols on 

suspended or benthic materials also plays a role 

in the amount of chlorophenols in water. Light 

chlorophenols are fixed to only a small extent, 

but pentachlorophenol adsorbs very strongly on 

certain types of particles when conditions are 

suitable. 

Terrestrial Environment. The persistence of 

chlorophenols in the soil depends on their 

adsorption-desorption characteristics. Only the 

adsorption of pentachlorophenol has been studied in depth. It attaches very strongly to earth 

and is not easily washed away by rain [67]. 

Atmosphere. The presence of chlorophenols 

in the atmosphere has been inferred from the 

detection of minute quantities of pentachlorophenol in rainwater and snow. 

10. Toxicology 

The toxicity of chlorophenols to animals depends upon the degree of chlorination, the positions of the chlorine atoms, and the purity of the 

sample. The LD50 values for rats are given in 

Table 3 [30]. In rats and rabbits, 50% of the 

administered dose of pentachlorophenol is eliminated within 24 h. In mice, 70-85 % ofthe dose 

is eliminated within 4 d. The elimination of tetrachlorophenols is comparable to that of pen: 

tachlorophenol [63]. 

Toxic doses of chlorophenols cause convulsions, as well as other symptoms [63]. Trembling 

and clonic convulsions can be induced by tactile 

or auditory stimulation. Agitation and polypnea 

are observed before muscular weakness; dyspnea 

and coma occur and finally death [37], [66]. The 

toxic effects of pentachlorophenol and the tetrachlorophenols are due to the inhibition of oxidative phosphorylation. 

Alter repealed administration, loxic doses of 

chlorophenols cause mainly hepatic and renal 

lesions. The no-effect doses were ca. 100 mg/kg 

for 2,4-dichlorophenol and 2,4,6-trichlorophenol and 1-5 mg/kg for pentachlorophenol [63]. 

Investigations of the elimination and metabolism of chlorophenols have been inconclusive. 

Dogs excrete 2-chlorophenol in the urine as both 

the free and conjugate forms (87%). However, 

with rabbits 2-chlorophenol is detected after the 

administration of chlorobenzene. 2,4-Dichlorophenol, 2,4,6-trichlorophenol, and traces of 

2,4,5-trichlorophenol are found in their free and 

conjugate forms, following the administration of 

/?- or y-hexachlorocyclohexane to mice. 

2,4,5-Trichlorophenol and its conjugate 

forms are found in the urine following 

Table 3. Lethal doses (LD50) of chlorophenols for rats 

Chlorophenol 

2-Chlorophenol 

3-Chlorophenol 

4-Chlorophenol 

2,4-Dichlorophcnol 

2,4,5-Trichlorophenol 

2,4,5-Trichlorophenol, sodium salt 

2,4,6-Trichlorophenol 

2,3,4,6-Tetrachlorophenol 

Pentachlorophenol 

Pentachlorophenol, sodium salt 

L D 5 0 . 

oral 

670 

570 

261 

580 

8;o 

•1620 

/82 0 

**'14« 

. 50 

210 

mg/kg 

percutaneous 

950 

1030 

1390 

1730 

2260 

210 

100 

72 
P.33 

8 Chlorophenols Vol. A 7 Vol. A 7 

the administration of 2,4,5-trichlorophenoxy-4'-

butyric acid to mice; 2,3,4,5-, 2,3,4,6-, and 

2,3,5,6-tetrachlorophenols, free and in their conjugate forms, are detected after the administration of pentachlorophenol [61]. 

Chronic effects of human exposure to low 

doses of chlorophenol have not been reported, 

but toxic doses of pentachlorophenol cause 

severe pathological modifications in the gastrointestinal tract, lungs, spleen, liver, kidneys, and 

cardiovascular system. Low levels of pentachlorophenol have been found in the urine, blood, 

and body fat of exposed and unexposed persons, 

but no explanation for their presence is available. Certain chlorophenols cause dermatoses 

such as photoallergic contact dermatitis, papulofollicular lesions, comedones, and sebaceous 

cysts [40], [41], [63], [68]. 

11. References 

[1] A. Laurent, Ann. Chim. Phys. 3 (1841) 195. 

[2] Grignard: Traite de chimie organigue, 1st ed., 1940, 

T6-915. 

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Chlorophenox 

Weed Control and Plant Ci 

MARGUERITE L. LENG. D O 

1. Production 

2. Quality Specifications . 

3. Uses 

Research on chlorii 

pounds during World Wa 

of the selective herbici 

chlorophenoxyacetic acid 

broadleaf weeds in gras: 

such as cereal grains, ric 

patents issued before 195C 

United States assigned t 

Paint Co. (Amchem. nov 

Dow Chemical [1]. 

Although all patents r 

new plant growth regu! 

have been developed, phi 

comprise a large sector o 

cide market. The estima 

manufacture of chlorop 

and derivatives approacl 

with a value of about $ 1.7 

production decreased ab( 

1983 because of weak pric 

The principal chlorot 

used as herbicides are lists 

Table 1. Chlorophenoxyalkam 

Common name 

2,4-D 

2,4-DB 

Dichlorprop 

MCPA" 

MCPB" 

Mecoprop" 

2,4,5-T 

Fenoprop 

Chemici 

(2,4-dich 

4-(2.4-dii 

2-(2.4-dii 

(4-chlorc 

4-(4-chlo 

2-(4-chlo 

(2,4,5-tri 

2-(2.4,5-i 

* Melting point data in Table 

nomenclature using 2-methyl--