P. 1 

# OAR Box 1877 Prepped by Keeia Richards



## Document

Number: 

# 41 ) ll-B-3 8 Docket Number: 

# A-90-1 9

Printed 12/2/200810:36:49AM

Sheet 41 of 46P. 2



### MEMORANDU M TO : FROM : DATE : Proces s Vent s Docke t A-90-1 9

Wand a Floy

d Decembe r 199 0 

# A-90-1 9 ll-B-3 8 

# PJXOL I SEP 4I99 2 EPAAIRDQCKF T SUBJECT : HONNESHAP : Industr yCharacteristics/Chlorophenol s Attache d i s a product-proces s summar y(PPS ) fo r the productio n o f Chlorophenol s vi a Hydrolysi s o f Chlorobenzen e category . Thi s PP S wa s develope d a s par t o f the Industria l Profil e projec t i n suppor t o f the Hazardou s Organi c NESHAP (HON ) regulator yeffort . Informatio n i n thi s PP S i s use d a s a basi s fo r emission s an d cos t impac t estimate s fo r the HO Nprogram . Liste d belo w ar e the ke yreference s use d i n developin g the attache d PPS . 198 9 Directory" f Chemica l Producer s USA . SR I International , California , p . 530 . Genhartz , Wolfgang , ed . Ullmann' s Encyclopedi a o f Industria l Chemistry , 5t h edition . VC H Publishers , Florida , 1985 . p . 1-8 .

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# Doognen f i s OOGIB I

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## Reviewer : 

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# 198 9 DIRECTOR

Y O F CHEMICA L PRODUCER S UNITE D STATE S O F AMERICA

Informatio n i n thi s Director y i s fo r th e tol a an d privat e U M o f sponsor s o f th e Director y o f Chemica l Producers Program .



# RADIA N LIBRAR Y RESEARC H TRIANGL E PARK , N CP.2 2 i ' '

33 3 RAVENSWOO D AVENU E MENL O PARK, CALIFORNI A 9402 5 

### (415)859-362 7 FAX : (415)326-551 2 

### TWX : 910-373-204 6 TELEX : 33448 6

Copyright ©

198 9 SR I International . Unauthorize d us e o rreproductio n o f al l o ran y par

t o f thi s documen t i s prohibited . Printe

d i n U. S A

««* •P.2 3 * 

# < V 198 9 DIRECTORY O F CHEMICA L PRODUCER S UNITE D STATE S PRODUCT S 1-Chk>ro-4-nitrobenzen e (Cont'd ) Monsant o Compan y Monsant o Chemica l Compan y Sauget , Illinoi s Source : SR I Internationa l estimate s as of Januar y 1 , 1989 . TOTA L Annua l Capacit y (Million s o

f Pounds ) 85 <M 5

Charle s City , Iow

a

Grea t Meadows , NewJersey Orem , Uta h Holley , Ne wYor k 2-Chloro-4-nitrobenzoi c aci d Solva y America , Inc . Salsbur y Laboratories , Inc. , subsidiar y Salsbur y Chemical s 4-Chloro-3-flitrobenzoi c aci d AMA X Inc . Clima x Metal s Company , subsidiar y Climax Molybdenu m Company , subsidiar y 4-Chloro-2-nitrophenylure a Paris h Chemica l Compan y 2-Chloro-S-nitropyridin e Dia z Chemica l Corporatio n 2-Chloro-4-nttrotoluen e (p-Nitro-o-chlorotoluene ) E . I . d u Pon t d e Nemours & Company , In c Chemical s an d Pigment s Departmen t Deepwater , Ne wJersey 1-Chlor o octadecan e (See : n-Octadecy l chloride ) 1-Chloro-octan e (See : n-Octy l chloride ) 1-Chloro-2-oxopropan e (See : Chloroacetone ) Chloroparaffin s (See.- Chlorinate d paraffins) Chloropentafluoroethan e (F-115 ) E . I . d u Pon t d e Nemours & Company , In c Chemical s an d Pigment s Departmen t Freon * Products Divisio n Deepwater , Ne wJerse y 5-Chloro-2-pentanon e Eastma n Koda k

Compan y Sterlin g Dru g Inc , divisio n Sterlin g Organic s Divisio n m-Chloroperoxybenzoi c aci d Aldric h Chemica l Company , Inc . /3-Chlorophenetol e R.S A Corporatio n m-Chloropheno l (3-Chlorophenol ) Hexago n Laboratories , Incorporate d Specialt y Organic s Inc . 3-Chlorophanol (See : m-Chlorophenol ) 2-Chlorophenothiazin e Chemica l Dynamic s Corporatio n SmithKlin e Beckma n Corporatio n SmithKlin e Chemical s Divisio n Rensselaer , Ne wYor k Milwaukee , Wisconsi n Ardsley , NewYor k Bronx , Ne wYor k Irwindale , Californi a
Sout h Plamfield , NewJerse y Conshohocken , Pennsylvani a 2-Chlorophenothiazin e 10-carboxyii c chlorid e R.S A Corporatio n Ardsley , Ne wYor k 1-[4-Chloro-phenoxy]-3,3-dimethyl-1-{1,2,4-triazo-1-yf ] butan-2-on e (See : Triadimefo n unde rPesticides) 3-[4-Chlorophenoxy]-1,2-propanedio l carbamat e (See: Chlorphenesi n carbamat

e unde rMedicina l (Pharmaceutical ) Chemicals ) 1-f4-Chloropheny l (See. - Chlorcyclizin e hydrochlorid e under Medicina l (Pharmaceutical ) Chemicals ) p-Chloropheny l acetonitril e (p-Chlorobenzy l cyanide ) Adron , In c Orbi s Product s Corp . Newark , NewJerse y 2-Chloropheny.amin e (See : o-Chloroaniline ) 3-Chlorophenylamin e (See : m-Chloroaniline ) 4-Chlorophenylamin e (See : p-Chloroaniline ) 4-Chloro-a-phenyr-o-cre«o l (See : o-Benzyr-p-chloropBeno l unde rPesticides ) m-Chloropheny l diethanolamin e (2,2'-{[3-Chlorophenyl ] imino ] bisethanol ) (N,N-0i-{2-hydroxyethyl ] m-chloroaniline ) Millike n & Co . Millike n Chemica l Divisio n Inman , Sout h Carolin a Quantu m Chemica l Corp . Emer y Divisio n Loc k Haven , Pennsylvani a p-Chlorophenyt-a-glycery i ethe r carbamat e (See : Chlorphenesi n carbamat

e unde rMedicina l (Pharmaceutical ) Chemicals ) 3-Chlorc-7-0-[2-phenylglycinamido}-3-cephem-4 - carboxyli c aci d (See : Cefaclo runde rMedicina l (Pharmaceutical) Chemicals ) p-Chloropheny l 2-hydroxyethy l sulfid e Paris h Chemica l Compan y Orem , Uta h 2,2'-{[3-Chlorophenyl ] imino ] bisethano l (See : m Chloropheny l diethanolamine ) p-Chloropheny l magnesiu m chlorid e M& T Chemical s In c Carrollton , Kentuck y 2-Chloro-4-phenylpheno l (4-Phenyl-2-chlorophenol ) DowChemica l U.S A Midland , Michiga n 3-Chloro-1-phenylpropen e (See : Cinnamy l chloride ) 4^hlorophenylseler>|r.yM>romid e SynMet . In c Memphis , Tennesse e 4-Chlorophenylseleneny l chlorid e SynMet , In c J Memphis . Tennesse e 4-Chlorophenylseleno l SynMe t In c Memphis . Tennesse e 1Kp^hlorophenyl8urfonyi}-3-propylure a (Se a Chlorpropamid e unde rMedicina l (Pharmaceutical ) Chemica w

53 0 SR I Internationa l

# Ullmann' s Encyclopedi a o f Industrial Chemistr y

Volume s A1-A28 : alphabeticall y arrange darticle s Volume s B1-B8 : basi c knowledg e 

# U

E : o i C Fift l Volun Abra s Editoria l Advisor

y Boar d Hans-Jiirge

n Arp e Hoechs tAktiengesellschaft . Federa l Republi c o f

German y 

### Erns t Bieker t Knol l AG , Federa l Republi c o f German y 

### H . Edwar dDavi s Universit y o f

Minnesota . US A 

### Hein z Gerren s BAS F Aktiengesellschaft . Federa l Republi c o f

German y 

### Ralp h H . Hirschman

n Merck , Sharp e & Dohme , US A 

### Tetsuj i Kametan

i Hosh i University . Japa n 

### Aki o Mitsutan i Nippo n Chetmec h Consulting , Japa n 

### Charle s Reec

e Imperia l Chemica l Industries . U K 

### Davi dP . Sheet z Do w Chemical . US A 

### Howar dE . Simmon s E . I . D u Pon td e Nemours . US A 

### Eberhar dWeis e Baye r AG , Federa l Republi c o f German y 

### Rudol f Wirt z Hoechs tAktiengesellschaft , J Federa l Republi c o f

German^ - 

### Hans-Rudolf

Wuthricrr' - Metallgesellschaf

tAG . Federaj , Republi c o f German y , j 

# Exec u Senioi Edito i Jame s

MOM MVol . A 1 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 Productio n Director : Maximilia n Montkowsk

i Productio n Manager : Myria mNothacke r Librar y o f Congres s Car dNo . 84-25-82 9 Deutsch e Bibliothek . Cataloguing-in-Publicatio n Data : Ullmann' s Encyclopedi ao f Industria l Chemistr

y / ed . Wolfgang Gerhart z .. . [ed . advisor y boar d Hans-Jiirge n Arp e ...]. - Weinheim ; DeerfieldBeach , Florida ; Basel : VC H Verlagsgesellschaf t Bi s 4 . Aufl . u . d . T. : Ullmann s Enzyklopadi e de r Technischen Chemi e NE : Gerhartz , Wolfgang [Hrsg.] ; Encyclopedi aof Industrial Chemistr

y Vol . A . Alphabeticall y arrange darticles . 1 . Abrasive s t o Aluminu mOxide . - 5th . completely rev . ed . - 1985 . ISB N 3-527-20101- 7 (Weinheim ) ISB N 0-89573-151- 7 (Deerfiel dBeach . Florida )

© VCH Verlagsgesellschaf t mbH , D-694 0 Weinheim(Federal Republi c of Germany) , 1985 . Distribution : VC

H Verlagsgesellschaft

, P.O . Bo x 1260/1280. D-694

0 Weinhei m(Federa l Republi c o f Germany ) US A an dCanada : VC

H Publishers . 30

3 N.W . 12t h Avenue . Deerfiel dBeach , F L 33441-170

5 (USA } Al l right s reserve d(includin g thos e of translatio n int o othe r

languages) . N o par t

d f thi s boo k ma y be reproduce di

n any for m- b y photoprint , microfilm , o r any othe r mean s - no r

transmitte do r

translate d int o amachin e languag e withou t writte n permissio n fro

mth e publishers . Registere dnames , trademarks , etc . use di n thi s boo k

an dno t specificall y marke dasiuc h ar e no t

to b e considere dunprotected . Cove r design : Wolfgang Schmid t Composition , printing , an dbookbinding : Graphische r Betrie b Konra dTriltsch , D-8700 Wurzburg Printe di n th e Federal Republi c of Germany About t Frit z L'llma : sa w th e ne e furnis h recir. ca l industr y in g famou s kno w ho w i Enzyklopddi born . Durin g i Encycloped

i intoaconci s sourc e o f ir . an dpractic ; Now . i n it s evident . Themo s th e Encyclot than i n th e thoug h ac e change , i t o : t:rship . tacil

i authors , ar

u Th e sub j clopeui aha

? the progres s Ne w topic s ! • discipline s tronics . ph

u Adde dem

p broa dconc e industrial ir . high cos t a : '.trial s an de tect the en v :utur e gen

e •.'n dpro c



# H IP.2 6

' ' , i 

### Vol . A 7 Chlorophenol s 

# Chlorophenol s .c .~.CY"' ~ FRANCOI S MULLER , Rhone-Poulenc , L e Pont-de-Claix , Franc e (Chaps . 1-9 ) Y ' LILIANE CAILLARD , Rhone-Poulenc , Courbevoie , Franc e (Chap . 10 ) 

# B H 1 ' • ^^^^^^^^^^^^^H :

1 . Physica

l Propertie s 1 2 . Chemica

l Propertie s 1 2.1 . Reaction s o

f th e Hydroxy l Grou p 1 2.2 . Electrophili c Substitutio n o f th e Ring ... . 2 2.3 . Nucleophili c Substitutio n o f th e Ring 2 2.4 . Oxidatio n Reaction s 3 3 . Productio n 3 3.1 . Mono- , Di- , andTrichlorophenol s wit h n o Chlorin e i

n aMet aPosition ; Tetra chlorophenols ; andPentachloropheno l ... . 3 3.2 . Mono- , Di- , andTrichlorophenol s wit h Chlorin e i n aMet aPositio n 4 In chlorophenol s th e aromati c rin g o f pheno l i s substitute dwit h on e t o five chlorin e atoms . LAUREN T discovere dthi s grou p o f compound s whe n h e chlorinate dcoa l ta r i n 183 6 [1] , [2] . Chlorophenol s ar e industriall y importan t be caus e o f thei r broa dspectru mo f

antimicrobia l propertie s an dthei r

use s a s fungicides , herbi cides , insecticides , ovicides , an dalgicides . A mix tur e o f tctrachlorophenol s an dpentachloro phenol . eithe r

a s suc h o r

a s salt s o r

esters , finds widesprea dus e a s apreservativ e fo r wood , glue , paint , vegetabl e fibers , an dleather . I n addition , chlorophenol s ar e widel y use da s intermediate s i n chemica l syntheses . 

### 1 . Physical Propertie s Importan t

characteristic s an dphysica l prop ertie s o f chlorophenol s ar e show n i n Table s 1 an d2 . Wit h th e exceptio n o f 2-chlorophenol , thes e compound s ar e soli da t ambien t tempera ture ; the y al l hav e stron g characteristi c odors . Severa l o f

the msublim e readily . The y ca n b e steam-distilled . Th e chlorophenol s ar e onl y slightl y solubl e i n water , bu t highl y solubl e i n alcohols . The y impar t

astrongl y disagreeabl e tast e t o drinkin g water . 4 . Analysi s 4 5 . Quality Specification s 5 6 . Economi c Aspect s 5 7 . Use s 5 8 . Storag e andTransportatio n 6 9 . Environmental Consideration s 6 9.1 . Toxicity t o Faun aandFlor a6 9.2 . Persistenc e i

n th e Environment

7 10 . Toxicolog y 7 11 . Reference s 8 

### 2. Chemica

l Propertie s Chlorophenol s ar e versatil e intermediate s i n chemica l synthese s becaus e bot h th e hydroxy l grou p an dth e aromati c rin g ca n reac t b y bot h electrophili c an dnucleophili c substitution . The y ar e readil y oxidized . 

### 2.1 . Reaction

s o f th e Hydroxy l Grou p Chlorophenol s ar e mor e acidi c tha n phe no l an dreadil y formsalt s wit h alkal i an d alkaline-eart h hydroxide s o r carbonate s o r

wit h amines . Thes e salt s ar e stabl e an dsolubl e i n water . Chlorophenol s readil y formester s o f bot h organi c an dminera l acid s [3]-[5] . Ester s suc h a s chloropheny l phosphates , carbamate s [6] , [7] , chloroformate s [8] , carbonates , an dlaurate s ar e widel y used . Pentachloropheny l 2-ethyl hexanoat e i s use da s atextil e preservative . Chlorophenol s ar e als o readilwp-alkylated , an dether s derive dfro maliphatic , aromatic , an d heterocycli c reagent s compris e abroa dclas s o f industria l product s [9] , [10] . One'o f th e mos t widel y know n i s 2,4-dichloropheno'jcyaceti c aci dP.2 7 Chlorophenol s Vol . A 7 Vol . A 7 Tabl e 1 . Characteristic s o f th e chlorophenol s Chloropheno l 2-Chloropheno l [95-57-8] 3-Chlorophcno l [108-43-0] 4-Chloropheno l [106-48-9] 2.3-Dichioropheno l [576-24-9] 2,4-Dichloropheno l [120-83-2] 2,5-Dichloropheno l [583-78-8] 2.6-Dichloropheno l [87-65-0] 3,4-Dichloropheno l [95-77-2] 3.5-Dichloropheno l [591-35-5] 2.3,5-Trichloropheno l [933-78-8] 2,4.5-Trichloropheno l [95-95-4] 2,4,6-Trichloropheno l [88-06-2] 2,3,4-Trichloropheno l [15950-66-0] 3,4.5-Trichloropheno l [609-19-8] 2.3.6-Trichloropheno l [933-75-5] 2,3.5.6-Telrachloropheno l [935-95-5] 2,3,4,6-Tetrachlorophenol[J«-90-2 ] 2,3,4,5-Tetrachlorophenol[490/-5/-i ] Pentachloropheno l [87-86-5] Formul a C 6 H,CI O C 6 H a C1 0 C 6 H 3 C1 0 C 6 H 4 C1 2 0 C 8 H 4 C1 2 0 C 6 H 4 C1 2 0 C 6 H 4 CI 2 0 C 6 H 4 CI 2 0 C 6 H 4 CI 2 0 C 6 H 3 C1, 0 C 6 H 3 C1 3 0 C 6 H 3 C1 3 0 C 6 H 3 C1 3 0 C.HjClj O C.HJCIJ O C 6 H 2 CI 4 0 C 6 H 2 C1 4 0 C 6 H 2 C1 4 0 C 6 HC1, 0 M,

128.5 6 128.5 6 128.5 6 163.00 163.00 163.00 163.00 163.00 163.00 197.4 5 197.4 5 197.4 5 197.4 5 197.4 5 197.4 5 231.8 9 231.8 9 231.8 9 266.3 4 mp, ° C

8. 7 32. 8 42. 8 5 8 4 5 5 9 6 6 6 5 6 8 6 2 6 8 6 8 83. 5 10 1 10 1 11 5 69-7 0 116-11 7 19 0 bp,°C

174. 5 21 6 21 7 20 6 21 0 21 0 220 25 3 23 3 248-24 9 245-24 6 24 6 subl . 27 5 27 2 subl . 16 4 ( 3 kPa ) subl . 309-31 0 P* .

8.5 2 8.9 7 9.3 7 7.7 1 7.9 0 7.5 1 6.7 8 8.62 8.2 5 6.7 2 5.9 9 6.9 7 7.5 5 5.8 0 5.0 3 5.2 2 5.6 4 4.7 4 Tabl e 2 . Physica

l propertie s o f

th e mos t importan t

chlorophenol s Propert y bp,°C a t 0.133 3 kP a a t 1.33 3 kP a a t 5.33 3 kP a a t L3.3 3 kP a a t 53.3 3 kP a Specifi c heat

a t 2 0 Heat o f formatio n Viscosit y a t 5 0 °C . Solubilit y i n wate r Flas h poin t

(closec °C , J mol" 1 K~ ' a t 5 0 °C , kJ/mo l mP a a t 2 0 cup ) s ° C g/ L > C 2-Chloro pheno l 1 2 5 1 8 2 106 15 0 17 2 18 5 2 28. 5 12 1 4-Chloro pheno l 5 0 9 2 12 5 15 0 19 0 177 198. 9 5 27. 1 8 4 2,4-Dichlo ropheno l 5 3 9 3 123 146 18 7 19 0 2.6 5 4. 5 11 3 2,6-Dichlo ropheno l 59. 5 10 1 131. 6 154. 6 197. 7 2,4,6-Tri chldropheno l 76. 5 120. 2 152. 2 177. 8 222. 5
0. 8 Penta chloropheno l 13 2 17 8

29 5 0.01 4

[95-75-7](2,4-D) , whic h i s stil l use d a s aselec tiv e herbicid e fo r

broadlea f

plant s [11]-[13 ] (-> • Chlorophenoxyalkanoi c Acids) . 

### 2.2 . Electrophili c Substitutio n o f the Aromati c Ring Electrophili c substitutio n i s favore d b y th e presenc e o f

chlorin e atom s o n th e aromati c nu cleus ; thus , mos t

chlorophenol s partak e i n th e standar d reactions , suc h a s alkylatio n [14] , acy lation , nitration , sulfonation , halogenation , [15] , [16] , carboxylation , an d condensatio n wit h alde hydes , e.g. , formaldehyde , chloral , glyoxyli c aci d [17]-[19] . 

### 2.3 . Nucleophili c Substitutio n o f the Aromati c Rin

g Nucleophili c substitutio n fo r on e o r mor e of th e chlorin e atoms , althoug h disfavore d b y th e presenc e of

th e othe r

chlorin e atoms , i s nevertheles s used widely . Th e hydrolyse s o f

2-chloropheno l an d 4 - chloropheno l wer

e use d at

on e tim

e to ob tai n pyrocatecho l [120-80-9]an d hydroquinon e [123-31-9], respectively . Th e ammonoiysj s of 2-chloropheno l o r

4-chloropheno l produce s 2 - aminopheno l o r

4-aminophenol , rejpechvely . Thi s typ e of

reactio n i s use d primaril y t o prepar e variou s substitute d dipheny l ethers , whic h serv e a s efficien

t herbicide s [20

] - [22] . Chlorophenol s ca n b e c chlorinate d alicycli c ketone s rophenol " [599-52-0]b y re a aqueou s aceti c acid . "Hex : pesticida

l propertie s an d i s h nil [2435-53-2]i

n th e presen lys t such a s sulfuri c acid .

2 U ci-J^c i ci-^xYc i c i c i 'Hezschloropheaal * 

### 2.4 . Oxidatio n Reactiot Lik e othe r

phenols , c h oxidized ; ai r

oxidatio n fo

r wherea s oxidatio n wit h hy d t o th e correspondin g c h Oxidatio n b y aperoxid e s aci d i n benzen e a t

8 0 ° C yi i (85 % yield ) [23] :

O H O H 

# 6" - 

# 6 C

3 . Productio n Ther e ar e tw o type s o t thos e wit h on e t o thre e chi c i n amet a( 3 o r

5 ) positio n thos e whic h hav e fou r o r an d (2 ) thos e wit h on e t o t a t leas t on e bein g i n amt. t o OH . 

### 3.1 . Mono- , Di- , an

d Ti wit h n o Chlorine i

n a I V Tetrachlorophenols ; an d Pentachlorophenol Th e mono- , di- , an d tri e hav e n o chlorin e ato mi n t h tio n relativ e t o O H ar e 2-ch l phenol , 2,4-dichlorophenol .A 7 p* . 8.5 2 8.9 7 9.3 7 7.7 1 7.9 0 7.5 1 6.7 8 8.6 2 8.2 5 6.7 2 5.9 9 6.9 7 7.5 5 5.8 0 5.0 3 5.2 2 5.6 4 4.7 4

hcno l

>r e of • y th e lever - i d4 - > ob - inon e ;i s of :es 2 - ively . epare serv e P.2 8



## l i i Vol . A 7 Chlorophenol s ca

n be converte dint o poly - chlorinate dalicycli c ketone s suc h a s "hexachlo - rophenol " [599-52-0]b

y reactio n o f

chlorin e i n aqueou s aceti c acid . "Hexachlorophenol " ha s pesticida l propertie s an di s hydrolyze dt o chlora - ni l [2435-53-2]in th e presenc e of a n acidi c cata - lys t suc h a s sulfuri c acid .

H-, 0 

### ci^X/ a 

# I I + ci'Yc^c i a c i 'Hexachloropheno l C1,JL,C 1

I f + 2 HC

I ci'YY v c i 0 

### 2.4 . Oxidatio n Reaction s Lik e othe r phenols , chlorophenol s ca n b e oxidized ; ai r

oxidatio n form s chloroquinones , whereas oxidatio n wit

h hydroge n peroxid e lead s t o th e correspondin g chlorinate ddiphenol . Oxidatio n b

y aperoxid e such a s perpropioni c aci di n benzene at

8 0 ° C yield s chlorodiphenol s (85 % yield

) [23] : O H 

# (S OH 

# 6 f O

H C l O

H 

### 3 . Productio n Ther e ar e tw o type s of

chlorophenols : (1 ) thos e wit h one t o thre e chlorin e atom s bu t non e i n ameta( 3 o r

5 ) positio n relativ e t o O H an d thos e whic

h hav e fou

r o r five chlorin e atoms , an d(2 ) thos e wit

h on e t o thre e chlorin e atoms , a t least on e bein g i

n amet apositio n relativ e t o OH . 

### 3.1 . Mono- , Di- , an

d Trichlorophenol s wit h n o Chlorine i

n a Met a Position ; Tetrachlorophenols ; an d Pentachlorophenol Th e mono- , di- , an d trichlorophenol s which hav e n o chlorin e ato mi

n th e met a( 3 o r

5 ) posi - tion relativ e to O H ar e 2-chlorophenol , 4-chloro - phenol , 2,4-dichlorophenol , 2,6-dichlorophenol , Chlorophenol s 3 an d2,4,6-trichlorophenol . Th e tetrachlorophe - nol s an d pentachloropheno l are als o include d wit h thi s type . Thes e compound s ar e obtaine db y the direc t chlorinatio n of

phenol . Th e chlorinatio n o

f melte dpheno l [108-95-2] usin g chlorin e ga s [7782-50-5]yield s amixture of orth o an dpar amonochlorophenol s wit h a n o/p rati o o f ca . 0.5 4 (35/65) , whic

h i s scarcely de - penden t o n temperature . Th e distributio n be - twee n th e tw o isomer s depend s especially on th e natur e of th e chlorinatio n reagent

an dthe char - acteristic s of

th e reactio n medium . Th e forma - tio n of 2-chloropheno l i s favoredb y a n aproti c nonpola r solvent medium , such a s hexane , car - bo n tetrachloride , o r

dichloroethane . Th e o/p rati o i s als o highe

r fo r reaction s wit

h alo w con - centratio n of

pheno l an d ahigh temperatur e [24] . Th e chlorinatio n of

a5 % solutio n of

phe - no l in perchloroethylen e a t 110° C in th e pres - enc e of 0.0 1 wt % diisopropylamin e [108-18-9] give s aver y hig h ojp ratio , ca . 1 5 [25] . Chlorina - tion s usin g aqueou s sodiu mhypochlorite [7681-52-9]at

p H 10 , tert-b\xty\ hypochlorit e [507-40-4]an d alkal i phenolate s disperse di n a n anhydrou s medium[26] , o r chlorin e i

n aceti c aci di n th e presenc e of

aceti c anhydrid e [108-24-7]als o favo

r th e formatio n of

2-chloro - pheno l [27] . Th e formatio n o f

4-chloropheno l i s favore d b y chlorinatio n i

n apola r medium , such a s ace - tonitrile , nitrobenzene , o r ether [28]—[31] . Sub - stitutio n i n th e par apositio n i s als o strongl y favore db y th e us e of

sulfuryl chlorid e [7791-25-5] a s achlorinatin g agent

{ojp = 0.35 ) [28] , [31] . Certai n organi c sulfides , e.g. , dipheny l sulfid e [139-66-2] , activate chlorinatio n an d favor sub - stitutio n at

th e par apositio n [32] . Chlorinatio n usin g copper(II ) chlorid e i n aqueou s hydrochlo - ric aci di n th e presenc e o f

oxyge n lead s t o 4-chloropheno l (almos t

100% ) [33] . Mono- , di- , an d trichlorophenol s ar e mad e industriall y b

y chlorinatio n o f

pheno l wit

h chlorin e ga s i

n amel t i n cast-iro n reactors . Th e isome r distributio n i

n th e produc t

ma y b e ad - juste dt o marke t

demand s by th e chlorinatio n leve l an dby recyclin g variou s intermediates . Th e yield , base do n chlorin e an d phenol , i s greater than 95% . Tetrachlorophenol s an d pentachloropheno l ar e produce dbatchwis e i n niclrf l reactor s b

y th e chlorinatio n of

les s halogenate dchloro - phenol s i n th e presenc e of

aluminu mtrichlorid e [7446-70-0]o r

iro n trichlorid e [7105-08-0].I I

, < Chlorophenol s O H O H Vol . A 7

O H X 

# 6 X 

# ' O

H O

H y a

C U a



### 3.2 . Mono- , Di- , an

d Trichlorophenol s wit h Chlorine i

n a Met a Positio n Th e mono- , di- , o r

trihalogenate dphenol s havin g a t leas t one chlorin e ato mi

n amet aposi tio n ar e 3-chlorophenol , 2,3-dichlorophenol , 2,5-dichlorophenol , 3,4-dichIorophenol , 3,5-di chlorophenol , 2,3,4-trichlorophenol , 3,4,5-tri chlorophenol , an d 2,3,6-trichlorophenol . Thes e compound s canno t

be obtaine db

y th e chlorinatio n o

f phenol , bu t

mus t be mad e b

y othe r type s of reactions , such a s hydrolysis , sul fonation , hydrodechlorination , hydroxylation , andalkylation . Hydrolysi s of chlorobenzene s ca

n be carrie d ou t i n alkalin e aqueou s media , wit h o r withou t th e presenc e of

coppe r salt s [34] . I t

ca n be don e i n the vapo r

phas e at 250-40 0 ° C o n phosphate s [35 ] o r o n silic aat

500-55 0 ° C [36] . Hydrolysi s i s mos t frequently carrie dou t

i n th e presenc e of methanoli c sodiu mo r

potassiu mat

150-200° C an d1.0-3. 0 MP a[37] , [38] . Sulfonation-Desulfonation . Sulfonatio n of chlorobenzene s followe

db y th e desulfonatio n of chlorobenzenesulfoni c acid s ca n b e usedt o pro duc e numerou s chlorophenol s [39]-[44] . Th e chlorobenzene s ar e sulfonate db y usin g 15-20 % oleu mat 60-8 0 °C . Th e subsequent desulfona tio n i s usually carrie dou t b y usin g 15-25 % aqueou s sodiumhydroxid e solutio n a t 180 — 220° C an d 1.5-3. 0 MPa

. Sandmeyc V Reaction. w-Chlorophcnol s ca n als o b e made b y diazotizatio n ofth e correspond in g chloroaniline s tha t

hav e bee n obtaine deither b y nitratio n o f

chlorobenzene s followedb y hy drogenatio n o r

b y chlorinatio n of

nitrobenzene s [42] . irher e i b => relativ e rat e constan t k z = 1090 ; * 4 = 1910 ; * 2 4 = 124 ; k'Zi = 8 1 *2. » - i6 - *2.4. e " °- 7

- *2.4. 6 " °- 9 Hydrodechlorination

. Hydrodechlorinatio n of polychlorophenol s produce s 3-chlorophcnols . Thi s reactio n ha s lon g bee n carrie dou t

either i n th e vapo r phas e at 300-350° C on a

n alumin a catalys t [45 ] o r i n th e liqui dphas e a

t 150-25 0 ° C an d15.0-20. 0 MPa , usually i n th e presenc e of sulfu r [46] , [47] . More recently , catalytic hydrodechlorination of

polychlorophenol s i

n organi c o r aqueou s medi awit

h apalladiu mcatalys t

wa s usedt o obtai n 3-chloropheno l an d 3,5-dichloro pheno l [48] . Hydrodechlorinatio n of polychloro phenol s wit

h hydriodi c aci di

n a n aqueou s o r organi c mediumha s als o bee n reporte d[49] . Hydroxylation . Hydroxylatio n of chloroben zene s give s amixture of

5 5 w t % 4-chlorophenol , 30-3 5 wt % 2-chlorophenol , an d 15wt % 3 - chloropheno l [50] . Hoc k Pheno l Synthesis . Th e propylen e alky latio n o f achlorobenzen e followedb y oxidatio n an ddecompositio n o

f th e hydroperoxid e in a

n aci dmediumproduce s th e correspondin g chlo ropheno l [46] , [51] . Th e physica

l propertie s o

f th e principal com mercia l chlorophenol s ar e give

n i n Tabl e 2 . 

### 4 . Analysi s Th e acidit y of th e pheno l functio n i

n chloro phenol s increase s wit

h increasin g chlorinatio n of th e benzene ring . Potentiometri c analysi s wit h either sod ain a n aqueou s mediu

mo r a n amin e i n a n organi c mediu

mis , ihcrcfore , suitable . Goo d sensitivit y i s obtaine db

y usin g cychjhexylamine i n ethylen e glycol monoethy l ethe r absolven t [53] , [54] . Chlorophenol s ar e difficul t t o -separat

e b y ga s chromatograph y becaus e of their4iig h acidi P.2 9 Vol . A 7 ty . However , th e ligh

t h i rate db y usin g a n acidi c s > column . Th e heav

y home only afte r the pheno l f

u mean s of methylation , ac

e phthalation . Trace s of

chl . termine da s thei r

trifluor c by ga s chromatograph y detectio n (limi t

of detect : [54] . Al l phenol s ar e c o reverse-phas e HPL C on i wit h C 1 8 species . Graft s o enabl e separation s base di natio n (th e retentio n tim

e U V (28 0 nm

) detectio n i s rometri c detectio n i s 10

( [55]-[58] . I Rspectrometr

y ca n c differen t isomers , whic

h 1600-400cm" ' [59] . Pr

e try ca n identif y mos t ot phenol s b y th e chemica

l s i thei r aromati c protons . F be identifie dafte

r th e p i complexedwit

h hexamet

h [680-31-9]. Carbon-1 3 rtha n proto n NMR , bu t

i t usefu l informatio n [60] . Th e individual chlor o fiedan ddetermine dwi

t mean s of ga s chromat . chemica l ionizatio n ma : chlorophenol s are first

c o fluorobenzy l ethe r

o r pe : derivatives . Th e analysi s thes e specie s becaus e of

t h tivit y [61] . Therma l o r

chemica l • phenol s ca

n produc e sub rious t o th e environment , benzoparadioxins , pol an dpolychlorophenoxy r Thes e substance s can b e wit h U V detecto r

at ase ; [50] , [52] . Determination : quir e tha t th e sampl e b e p majo r portio n of

th e chen sampl e i s first

extracte d diu mwit h hexane an d th

e min aliqui dchromatogr a Th e chose n compou n edint o homologou s grou i minatio n i s mad e b

y usingP.3 0 )l . A 7 Vol . A 7 

### Chlorophenol s

atio n .'nols . ie ri n :min a 5 0 ° C c e o fydrogani c t wa s loro - loro - i s o r >1 .

ilky - itio n n a n :hlo - ty . However , th e ligh t homolog s ca

n be sepa - rate db y using a n acidi c soli dsupport

i n aglas s column . Th e heav

y homolog s ca

n be separate d onl y afte r the pheno l functio n i s blocke db y mean s o f methylation , acetylation , silylation , o r phthalation . Trace s of

chlorophenol s ma

y b e de - termineda s their

trifluoroacetylate dderivative s b y ga s chromatograph y wit h electro n captur e detectio n (limit

of detectio n ca . 2

0 mg/L ) [52] , [54] . Al l phenol s ar e correctl y separate db y reverse-phas e HPL C on asilic acolum n grafte d wit h C, 8 species . Graft s of

th e propylamin o typ e enabl e separation s basedon the degre e of chlori - natio n (th e retentio n tim

e depend s o n th e pKJ. U V (28 0 nm

) detectio n i s normall y used ; ampe - rometri c detectio n i s 10

0 time s mor

e sensitiv e [55]-[58] , I Rspectrometr

y ca n distinguis h betwee

n th e differen t isomers , whic

h absor b i n th e regio n 1600-40 0 cm" 1 [59] . Proto n NM Rspectrome - tr y ca n identif y mos t o f th e differen

t chloro - phenol s b y th e chemica

l shif t an dth e couplin g o

f thei r aromati c protons . Pentachloropheno l ca n b e identifiedafte

r th e pheno l grou p ha s bee n complexe dwit h hexamethylphosphori c triamid e [680-31-9]. Carbon-1 3 NM Ri s les s sensitiv e tha n proto n NMR , bu t

i t ca n provid e eve

n more usefu l informatio n [60] . Th e individua

l chlorophenol s ca

n b e identi - fie dan ddetermine dwit

h grea t sensitivit y b y mean s o f ga s chromatograph y followedb y chemica l ionizatio n mas s spectrometry . Th e chlorophenol s ar e first

converte dto thei r

penta - fluorobenzyl ethe r

o r pentafluorobenzoi c ester derivatives . Th e analysi s i s the n carrie dou t o n thes e specie s becaus e of

thei r highe r electronega - tivit y [61] . Therma l o r chemica l degradatio n of

chloro - phenol s ca n produc e substance s tha t ar e delete - rious t o th e environment . Certai n polychlorodi - benzoparadioxins , polychlorodibenzofurans , an dpolychlorophenoxyphenol s ar e examples . These substance s ca

n b e determine db

y HPL C wit h U V detecto r

a t asensitivit

y of ca . 1 mg/kg [50] , [52] . Determination s a t th e |xg/k g leve l re - quir e tha t th e sampl e b e pretreate dt o remov e th e majo r portio n of

th e chemica

l interferences . Th e sampl e i s first extracte dfro

ma n alkalin e me - diu mwit h hexan e an dthe n separate do n a n alu - min aliqui dchromatograph y column . Th e chosen compound s ca

n then be collect - e dinto homologou s group s [62] . Th e final deter - minatio n i s mad e b

y usin g G C wit

h electro n cap - ture detectio n o r b y combine dga s chromatogra - ph y an dmas s spectrometry . Th e limi t o f detec - tio n fo r 2,3,7,8-tetrachlorodibenzo-/wra-dioxi n [1746-01-6](TCDD ) i s les s than < 1 ng/kg [52] . 

## 5 . Qualit y Specification s Th e minimumassa

y fo r commercia

l chloro - phenol s i s 98. 5 wt% . Mor e ofte n than not , i

t i s >99wt % an da t

time s eve

n 99. 5 wt% . Th e APH A colo r

number i s alway s < 100 . Th e prin - cipa l impuritie s are othe r

isomer s of

the chloro - pheno l o r chlorophenol s wit

h mor e o r fewe r chlorin e atoms . I

n th e majorit

y o f cases , th e 2,4,5-trichloropheno l conten t i s < 2 0 mg/kg . Th e absenc e of

chlorobenzoparadioxins , chloro - benzofuran , an dmos t

ofte n chlorobenzene s shoul dbe noted . Polychlorophenoxyphenol s ar e the majo r impurit y (up to severa

l percent) i

n the heav

y chlorophenols , whic

h are markete da s mixture s of tetrachlorophenol s an dpentachlorophenol . Trac e quantitie s of

chlorobenzoparadioxin s an d chlorobenzofuran ar e als o found . Th e highl y toxi c compoun d2,3,7,8-tetrachlorodibenzo - para-dioxi n ha s neve

r bee n detecte di

n product s mad e b y chlorinatio n [52] . Th e sodiumsalt s o f th e heav y chlorophenol s contai n th e sam e impu - ritie s a s th e paren t

compounds . 

## 6 . Economic Aspect s Th e worl dmarket , excludin g th e Comeco n countrie s an dChina , i s fairl y stabl e an di s ca . 10 0 kt/a . Th e productio n of

heav y chlorophenol s i s 25-3 0 kt/a . O

f thi s 16-2 0 kt/ ai s produce di n th e Unite dState s (Vulcan , Reichhold) , 8 - 1 0 kt/ ai n Wester n Europ e (Rhone-Poulenc , Dynami t Nobel) , an d2 kt/ aelsewher e i n th e West . Productio n of

ligh t chlorophenol s i s ca . 6 0 kt/a . O f this , 18-2 0 kt/ ai s mad e i

n th e Unite d State s (Dow ) an d3 0 kt/ ai n Wester n Europ e (Rhone-Poulenc , BASF , Coalite , Bayer , Chemi e Linz , Esbjerg , KVK) . 

### 7 . Use s 

# <

Y Chlorophenol s ar e use

da s agricultural chem - icals , pharmaceuticals , biocides , an ddyes .6 Chlorophenol s

Agricultura

l Chemicals . Th e preparatio n of agricultural chemical s consume s 80-90% ) of chloropheno l production . Th e annua l consump tio n of th e herbicide s 2,4-dichlorophenoxyaceti c aci d(2,4-D ) an d2,4-dichlorophenoxy-4-butyri c aci di s 30-4 0 kt . Hoelo n (Hoechst) , Modow n (Mobil) , Ronstar

(Rhone-Poulenc) , an dTO K E 2 5 (Roh man dHaas ) ar e amon g th e majorherbicides. Curacro n (Cib aGeigy ) exemplifie s th e insecticides made fro

mchlorophenols . Amon g th e fungicides are Bayleto n (Bayer) , M O (Mitsu i Toats u Chemicals) , an dProclora z o r Sporta k (Boots) . Pharmaceuticals . Pharmaceutical s derive d fro mchlorophenol s includ e clofibrate , ethy l 2-(4-chlorophenoxy)-2-methylpropionat e (ICI) , usedi n th e treatmen t

fo r high serumcholesterol , an dMerva

n o r Aldofene , a

n antiinflammator

y an danalgesi c dru g (Continenta l Pharma) . Biocides . Biocide s tha t

are base do n chloro phenol s include th e molluscicide Bayluscide (Bayer ) an dth e bactericid e Santophe n o r Chlo rophe n (Monsanto) . Pentachloropheno l i s als o usedt o mak

e woo dan dcellulos e preservatives , ester s fo r th e textil e an dleather industries , paints , varnishes , an dorgani c adhesives . Th e sodiu msal t

of pentachloropheno l i s a

n active , water-solubl e material . I t i s use da s apre servativ e fo

r such organi c material s a s freshl y sawn woo d(agains t

blu e rot) , paints , adhesives , textiles , leather , an dfurs . Dyes . Chlorophenol s ar e use di n th e synthe si s o f anthraquinon e dye s (- * Anthraquinon e Dye s an dIntermediates) . Quinizarin , 1,4-dihy droxy-9,10-anthracenedion e [81-64-1], i s th e mos t importan t

example . 

### 8 . Storag e an

d Transportatio n Th e production , storage , transportation , an d us e of chlorophenol s ar e subjec t t o regulation s an dstipulation s tha t

depen don th e product s an d on th e countrie s concerned . Withi n th e EEC , di rectiv e 67/54 8 govern s classification , packing , an dlabeling ; directiv e "131 " 76/464 cover s dis charge s fro

mproductio n plant s int o aquati c me dia ; directive s 77/72 8 an d78/63 1 regulate th e rel evan t paint s an dpesticides , respectively . Vol . A 7 Transportatio n of

chlorophenol s i s governe d b y internationa l regulation s suc h a s IMD G Cod e (sea) , IATA-DG R(air) , RI D (rail) , an d AD R(road) . 

### 9 . Environmenta

l Consideration s Chlorophenol s are hazardou s to the environ ment an dhav e bee

n th e subjec t

o f numerou s eco logica l survey s of

faun aan dflor

ai n aquatic , ter restrial , an daerial environment s [63] . 9.1 . Toxicit y t o Faun a an d Flor a Microorganisms . Al

l chlorophenol s posses s bactericidal activitie s tha t increas e wit

h the de gree o f chlorinatio n an dattai n amaximumfo r the trichlorophenols . Their metaboli c effect

s include enzym

e inhibition s of

oxidativ e phos phorylatio n an dth e synthesi s of adenosin e tri phosphate . Chlorophenol s ar e highly toxi c to al gae . Trichlorophenol s ar e at leas t 10 0 time s mor

e toxi c tha n dichlorophenols , an dpentachloro pheno l i s useda s a

n algicide . Plants . Chlorophenol s posses s aphytotoxic it y tha t increase s wit

h th e degre e of

chlorination . Th e absorptio n of

chlorophenol s b

y plant s de pend s on th e solubilit

y of th e produc t

an dp H of th e environment . Terrestrial an daquati c plant s ca n i n certai n case s absorb , transform , an delimi nate chlorophenol s withou t harm , bu t

mos t often thes e plant s ar e ver

y sensitiv e to th e phyto toxicit y of chlorophenols . Aquati c Organisms . Fis h andothe r aquati c organism s absor

b chlorophenol s throug h their gills , gastrointestina l tract , o r skin . Measure ment s ove r 2- 4 dsho w tha t

acute toxicit

y fo r invertebrates , Crustacea , an dfreshwate r an dseawater fish increase s wit

h th e leve l o f chlorina tion . Fo r mono- , di- , an dtrichlorophenols , the 2- 4 dLC J 0 i s 0.6-10. 3 mg/L , dependin g o n th e species . Fo r

pentachlorophenol , i

t i s 0.03 - 0. 6 mg/L , excep t

fo r certai n resistan t

inverte brate s tha t

ca n surviv e concentration s *o f 5 - 1 0 mg/L . • " Chlorophenol s als o hav e along-^rrn^toxi c effec t at lo w concentrations . 2,4-Dichlqropheno l an d2,4,6-trichloropheno l a t concentration s of 6.2-10. 3 mg/

L affec t th e fertilizatio n of

se aur P.3 1

Vol . A 7 chi n eggs , an dpentachloro i an dhepati c lesion s in fish mend s tha t

th e maximu

ma pheno l concentratio n i

n su r ceed0.05 5 mg/L . Fo r

2,4- c 2-chlorophenol , the EP

A se t centration s at

2.020 an d4.3 8 [64] . Thi s limitation , base dc thene dby th e fac

t tha t chic mulat e t o only asmall exte i 

### 9.2 . Persistenc

e i n th e I Aquati c Environment . C

h presen t in th e aquati c en ' forms . They ma

y be disso l plexedform , adsorbe don s o r biologica l material s o r

b carrie di n biologica

l tissue s b y biodegradation , photod c lizatio n t o th e atmosphere , Biodegradation i s th e [ whic h chlorophenol s ar e r t induce dbecaus e th e antim i thes e product s require tha t Biodegradatio n i s rapi dwh < ganism s ar e already preser . pheno l i s more difficult.to othe r chlorophenols . Chlorophenol s photode pose dt o U

V light , such a s s surface . Volatilization transfer s fro mth e water

to th e ai r b u affec t it . Th e adsorption o suspende do r

benthi c mate r i n th e amoun t

o f chloroph e chlorophenol s are fixedt o bu t pentachloropheno l ads c certai n type s of

particle s \ suitable . Terrestria l Environment . chlorophenol s i

n th e soil adsorption-desorptio n cha : adsorptio n o

f pentachloro p ie di n depth . It

attache s v

e an di s no t easil y washe dau Atmosphere

. Th e presen i n th e atmospher e ha s be e detectio n of

minute quanti pheno l i n rainwate r

an dsn >/Ol . A 7 Vol . A 7 Chlorophenol s overne d IMD G iii) , an d

I S ;nviron ouseco atic , ter y

| | 

# I

: : <

posses s the de nu mfo r el l eel s c phos - •sin e iri di c to al le s more ichloro - 1 totoxic - "ination . [\ ant s de - ;

j i dp H o f ? j c plant s * | idelimi - ; i mos t of - i ] e phyto - ; )

: • ) aquati c '

j g h their 'leasure icit y fo r an dsea hlorina lols , th e g on th e s 0.03 - •

; inverte - , s o f 5 - :" j chin eggs , an d pentachloropheno l cause s rena l an dhepati c lesion s in fish. Th e EPA recom mend s tha t

th e maximumaverag e pentachloro pheno l concentratio n in surfac e water s no t ex cee d0.05 5 mg/L . Fo r

2,4-dichloropheno l an d 2-chlorophenol , th e EP

A se t th e maximumcon centration s at

2.020 an d4.38 0 mg/L , respectively [64] . Thi s limitation , base do n toxicity , i s streng thenedb y th e fac t tha t chlorophenol s bioaccu mulat e t o only asmall extent

[65] , [66] . 

### 9.2 . Persistenc e in th e Environmen t Aquati c Environment . Chlorophenol s ma y b e presen t i n th e aquati c environmen t i n man y forms . The

y ma y b e dissolve di

n fre e o r com plexe dform , adsorbe don suspende diner t soli d o r biologica l material s o r

benthi c sediments , o r carrie di n biologica

l tissues . The y ar e remove d b y biodcgradalion . photodccomposilion , volati lization to the atmosphere , an d adsorption . Biodegradation i s th e principal mean s b y whic h chlorophenol s ar e removed . I t mus t be inducedbecaus e th e antimicrobia l activitie s of thes e product s require tha t th e bacteri aadapt . Biodegradatio n i s rapi dwhe n adapte dmicroor ganism s are already present , bu t pentachloro pheno l i s mor

e difficul t t o biodegrad e than th e other chlorophenols . Chlorophenol s photodecompose whe n ex pose dt o U V light , such a s sunlight

o n th e water surface . Volatilization transfer s th e chloropheno l fro mthe water

t o th e ai r bu t doe s no t otherwis e affec t it . Th e adsorption o

f chlorophenol s o n suspendedo r

benthi c material s als o play s arol e i n the amoun t

o f chlorophenol s i

n water . Light chlorophenol s are fixedt o only asmall extent , bu t pentachloropheno l adsorb s ver y strongl y o n certain type s of

particle s whe

n condition s ar e suitable . Terrestrial Environment . Th e persistenc e of chlorophenol s i

n th e soi l depend s on their adsorption-desorptio n characteristics . Onl y th e adsorptio n of

pentachloropheno l ha s bee n stud ie di n depth . I t

attache s ver

y strongl y t o earth an di s no t easil y washe dawa

y b y rai n [67] . Atmosphere . Th e presenc e o f chlorophenol s i n th e atmospher e ha s been inferre dfro mth e detectio n of

minut e quantitie s o f

pentachloro phenol i n rainwate r

an d snow . 

### 10 . Toxicolog y Th e toxicit

y of chlorophenol s to animal s de pend s upo n th e degre e o

f chlorination , th e posi tion s of th e chlorin e atoms , an dth e purity o f th e sample . Th e LD 5 0 value s fo r rat s are give

n i n Tabl e 3 [30] . In rat s an d rabbits , 50 % of th e administere ddos e o

f pentachloropheno l i s elimi nate dwithi n 2

4 h . I n mice , 70-8 5 % ofth e dos e i s eliminate dwithi n 4 d . Th e eliminatio n of tet rachlorophenol s i s comparabl e t o that o f pen : tachloropheno l [63] . Toxi c dose s o

f chlorophenol s caus e convul sions , a s wel

l a s othe r symptom s [63] . Tremblin g an dcloni c convulsion s ca

n b e induce db

y tactil e o r auditory stimulation . Agitatio n an dpolypne a ar e observe dbefor

e muscula r weakness ; dyspne a an dcom aoccur

an dfinall y death [37] , [66] . Th e toxi c effect

s o f pentachloropheno l an d th e tet rachlorophenol s are du e to th e inhibitio n o f oxi dativ e phosphorylation . Alter repeale dadministration , loxi c dose s o f chlorophenol s caus e mainly hepati c an d rena l lesions . Th e no-effect

dose s wer

e ca . 10 0 mg/kg fo r 2,4-dichloropheno l an d 2,4,6-trichlorophe no l an d1- 5 mg/kg fo

r pentachloropheno l [63] . Investigation s of

th e eliminatio n an d meta bolis mo f chlorophenol s hav e bee

n inconclusive . Dog s excret

e 2-chloropheno l in th e urin e a s bot h th e fre e an d conjugate form s (87%) . However , wit h rabbit s 2-chloropheno l i s detecte dafte r th e administratio n of

chlorobenzene . 2,4-Dichloro phenol , 2,4,6-trichlorophenol , an d trace s o f 2,4,5-trichloropheno l are foundin their fre e an d conjugate forms , following th e administratio n of /? - o r y-hexachlorocyclohexan e t o mice . 2,4,5-Trichloropheno l an d it s conjugate form s ar e foundi

n th e urin e following Tabl e 3 . Letha l dose s (LD 50 ) o f chlorophenol s for

rat s Chloropheno l 2-Chloropheno l 3-Chloropheno l 4-Chloropheno l 2,4-Dichlorophcno l 2,4,5-Trichloropheno l 2,4,5-Trichlorophenol , sodiu msal t 2,4,6-Trichloropheno l 2,3,4,6-Tetrachloropheno l Pentachloropheno l Pentachlorophenol , sodiu msal t L D 5 0 . ora l 67 0 57 0 26 1 58 0 8; o •162 0 /82 0 **'14 «

. 5 0 21 0 mg/k g

percu taneou s 95 0 103 0 139 0 173 0 226 0 21 0 10 0 7 2P.3 3

8 Chlorophenol s Vol . A 7 Vol . A 7 th e administratio n of

2,4,5-trichlorophenoxy-4' - butyri c aci dt o mice ; 2,3,4,5- , 2,3,4,6- , an d 2,3,5,6-tetrachlorophenols , fre e an di n thei r con jugat e forms , ar e detecte dafte r th e administra tio n of pentachloropheno l [61] . Chroni c effect

s o f human exposure t o low dose s o f chloropheno l hav e no t

been reported , bu t toxi c dose s of

pentachloropheno l caus e sever e pathological modification s i n th e gastro intestinal tract , lungs , spleen , liver , kidneys , an d cardiovascula

r system . Low level s of

pentachlo ropheno l hav e bee

n foundi n th e urine , blood , an dbod y fa t o f expose dan dunexpose dpersons , but no explanatio n fo

r their presenc e i s avail able . Certai n chlorophenol s caus e dermatose s such a s photoallergi c contac t dermatitis , papulo follicula r lesions , comedones , an dsebaceou s cyst s [40] , [41] , [63] , [68] . 

## 11 . Reference s [1 ] A . Laurent , Ann. Chim. Phys. 3 (1841 ) 195 . [2 ] Grignard : Traite de chimie organigue, 1st ed. , 1940 , T6-915 . [3 ] Velsico l Chemical , U S 4226813 , 197 9 (J . A . Al bright) . [4] Do w Chemical , U S 4 33 4 111 , 197 8 (R.A . Davis) . [5 ] Synthelabo , F R247 5 543 , 198 0 (J . P . Kaplan) . [6 ] ANVAR , F R248 7 343 , 198 0 (J . Martinez) . [7 ] Hitach i Manell , JP81/10521 , 197 9 (N . Ogoshi) . [8 ] Bayer , D E 301 9 526 , 198 0 (G . Rauchschwalbe) . [9] Spof aUnite dPharma , U S 422 1 919 , 1975 ; C S 8681 , 1974 . [10 ] Rhone-Poulenc , EP4 6 719 , 198 0 (S . Ratton) . (11 ) UBE , J P 80/62033 , 197 8 (Y . Umemura) . [12] VEB Berli n Chemie , D E 290 3 343 , 197 9 (E . Gores) . [13 ] PPG , U S 4 29 3 707 , 197 9 (S . B . Richter) . [14] Coalite , EP49126 , 1980 ; GB31041 , 198 0 (K . Glad win) . [15 ] Akad . Wiss . DDR , D D 142333 , 197 9 (D . Marlin) . [16] Cib aGeigy , U S 4 22 3 166 , 197 7 (R . Jaeger) . [17 ] Nippo n Syntheti c Chem. , J P 81/5 5 337 , 197 9 (K . Nakashima) . [18 ] Nippo n Syntheti c Chem. , J P 81/5 5 338 , 197 9 (K . Gougi) . [19 ] Nippo n Syntheti c Chem. , J P 81/5 5 339 , 197 9 (K . Nakashima) . [20 ] ICI . U S 424 2 121 . 197 6 (A . F . Hawkins) . [21 ] UBIi , U

P 2 3 725 . 1980 : Jl'79/99914 , 197 9 (H . Sckio ka) . [22] Do w Chemical , U S 433 2 820 , 198 0 (D . M . Lowell) . [23 ] Bayer , D E 2 65 8 866 , 197 6 (H . Seifert) . [24] W . D . Watson , / . Org. Chem. 3 9 (1974 ) no . 8 , 1161 . [25 ] Cib aGeigy , D E 3 31 8 791 , 1983 ; C H 3234 , 198 2 (I . Szekely) . [26 ] Y . Ogat ae t

al. , J. Chem. Soc. Perkin Trans. 2 1984 , no . 3 , 451 . [27 ] Y . Furuya , Chem. Ind. London 1976 , no . 15 , 649 . (28 ) A . Campbell , D . J . Shields , Tetrahedron 2 1 (1965 ) 211 . [29 ] S . U . Zubare v et

al „ / . Org. Chem. USSR (Engl. Transt.) 4 (1968 ) no . 10 , 1769 . [30 ] Registry of

Toxic Effecis of

Chemical

Substances 1981-1982. Cincinnati , Ohio , 4 5 226 , Jun e 1983 . [31 ] W . D . Watson , J. Org. Chem. S O (1985 ) 245 . [32] W . D . Watson , Tetrahedron Lett. 1976 , no. 30 , 2591 . [33 ] H . P . Crocker , R . Walser , J. Chem. Soc. 1 4 (1982 ) 1970 . [34] Bayer , D E 2259433 , 1974 (K . Wedemeyer) . [35 ] A . H . Haymob , Zh. Obshch. Khim. 2 6 (1956 ) 1647-1650 . [36] A . Galat , / . Am. Chem. Soc. 7 4 (1952 ) 3890-3891 . [37 ] Rep. Gov. Chem. Ind. Res. Inst. Tokyo 4 7 (1952 ) 327-336 . [38 ] Velsico l Chemical , U S 4094913 , 1977 (A . W . Carl son) . [39 ] Do w Chemical , U S 283 5 707 , 195 6 (W . C . Stoesser) . [40 ] Notices d'information medicate sur les affections figurant ilan.i la lisle eurapeenne des maladies professioniwlIcs 23/7/196 2 an d20/7/1966 , Commissio n de s Com munuutc s Europccnncs , cd . 1969 . [41 ] J . C . Limasset

e l al. , Chlorophenols et

dioxines: risques pour les travailleurs de I'industrie chimique et pour les utilisateurs. INR S Cahie r d e note s documentaire s 1980 , not e N D 1249-99-80 . [42] V . D . Simonove t

al. , Zh. Prikl. Khim. (Leningrad) 4 5 (1972 ) no. 12 , 2765 . [43 ] Rhone-Progil , FR2212827 , 197 2 (G . Soula) . [44 ] Reichhol dChemicals , G B 84 5 287 , 195 6 (F.J . Shel ton) . [45 ] Progil , F R216 1 861 , 197 1 (G . Rivier) . [46 ] Bayer , D E 2443152 , 197 4 (K . Wedemeyer) . [47 ] Bayer , D E 2344925 , 197 2 (W . Kiel) . [48 ] Rhone-Poulenc , EP55196 , 1980 ; EP55197 , 1980 ; E P 5 5 198 , 198 0 (G . Cordier) . [49 ] Rhone-Poulenc , EP 118377 , 198 3 (G . Cordier) . [50] L . Castl e e t

al. , / . Chem. Soc. Chem. Commun. 1978 , no . 16 , 704 . [51 ] M . I . Farabero v e t

al „ Zh. Prikl. Khim. 3 9 (1966 ) no . 9 , 2094-3101 . [52] Rhone-Poulenc , interna l report . [53 ] W . Selig , Mikrochim. Acta 2 (1971 ) no . 3-4 , 359 . [54 ] K . Abrahamsson , T . Mi n Xie , J. Chromatogr. 27 9 (1983 ) 199 . [55 ] K . Ugland , / . Chromatogr. 21 3 (1981 ) 83-90 . [56] J . Nai r

e t al. , / . Liq. Chromatogr. 6 (1983 ) no. 14 , 2829-2837 . [57 ] N . G . Buckma

n c l al. . J. Chromatogr. 284 (1984 ) 441-446 . [58 ] R . Beauchamp , P . Boinay , J. Chromatogr. 204 (1981 ) 123-130 . [59 ] L . J . Bellamy : The Infra Red Spectra of

ComplexMolecules, Chapma n & Hall , Londo n 1975 . [60 ] M . T . Tribble , J . G . Traynham , / . Am. Chem. Soc. 9 1 (1969 ) no . 21 , 379-388 . [61 ] S . S . Zhi , A . H . Dufficld . J. Chromatogr. 284 (1984 ) 157-165 . [62] H . R . Buser , / . Chromatogr. 10 7 (1975 ) 295-310 . [63 ] V . P . Kozak

e t al. , Reviews of

the Environmental

Effects of Pollutants - XI

Chlorophenols - Repor t

EPA - 600/1-179-012 . [64] K . L . E . Kaiser , Can. J. Chem. 60 (1982 ) no. 16 , 2104 . [65 ] Fed. Regist. 4 5 (1980 ) no . 231 , 7 9 318 . [66 ] K . Kobayashi , Nippon Suisan Gakkatslii 4 5 (1979 ) no . 2, 173 . 4- - [67 ] M . Alexander , M I . H . Aleem , J. Agric". Fool Chem. 9 (1961)44-47 . [68 ] INRS , Cahie r

d e note s documentaire s 1984 , fiche toxi cologiqu e no . 196 . - , 

# Chloropheno x Weed Control and Plant Ci MARGUERIT E L . LENG . D O 1 . Productio n 2 . Qualit y Specification s . 3 . Use s Researc h on chlori i pound s durin g Worl dW

a of th e selectiv e herbici chlorophenoxyaceti c aci d broadlea f weed s i n gras : such a s cerea

l grains , ric patent s issue dbefor

e 195 C Unite dState s assigne dt Pain t Co . (Amchem . no

v Do w Chemica

l [1] . Althoug h all patent s r ne w plan t growt h regu ! hav e bee n developed , ph

i compris e alarg e secto r

o cide market . Th e estim a manufactur e o

f chloro p an dderivative s approac l wit h avalu e o

f abou t $ 1. 7 productio n decrease dab ( 198 3 becaus e o

f wea k pri c Th e principal

chlorot used as herbicides ar e lists Tabl e 1 . Chlorophenoxyalka m Commo n nam e 2,4- D 2,4-D B Dichlorpro p MCPA " MCPB " Mecoprop " 2,4,5- T Fenopro p Chemic i

(2,4-dic h 4-(2.4-di i 2-(2.4-di i (4-chlor c 4-(4-chl o 2-(4-chl o (2,4,5-tr i 2-(2.4,5- i * Meltin g poin t

dat ai n Tabl e nomenclatur e usin g 2-methyl- -