Document jg9yXq2xo6yDavp2zRdY8gMGN

ATTORNEY WORK PRODUCT 2,4-Dichlorophenoxyacetic Ac id(2,4-D) Ref: (1) Tent. Proc. for 2,4-D Job No. 155-5018 4/4/46 (2) Description of Pro duct s-Nitro Plant 12/13/41 On December 6, 1948, the manufacture of 2,4-D was started in Building 79 of the Nitro plant at an estimated rate of 300,000 lbs. per month. This oper ation was of limited duration, since 2,4-D was regularly produced at the Krummrich and Queeny plants at that time. The process was essentially the same as that run at these plants. Chemical Reactions: A, Basic Process Step 1 - Condensation Reaction ,C1 w + ClCH2C00Na + NaOH 1*S hrs. 0CH2C00Na 2,4-Dichlorophenol (produced at Krummrich by chlorination of phenol) Sodium chloroacetate (Purchased from Dow) Sodium 2,4-dichlorophenoxyacetate , (Na 2,4-D) + NaCl Sodium chloride + H20 tT ,, Water Step 2 - Acidification .Cl 2 Cl-</ X'>0CH2C00Na H 2S4 Cl 95 > 2 C l - ( O / " 0CH9C00H + Na2S04 15-30 min. Sulfuric acid 24-D * Sodium sulfate Step 3 - 2,4-Dichlorophenol Recovery 2 Cl-^_VONa + H2S04 Sodium 2,4-dichlorophenate (present in condensa- tion reaction mother liquor) CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER, > 2C1-V V Na2S04 2 ,4-dichlorophenol (recycled to conden- sation reaction) HCG 11/21/83 HO f< i Ai*kTi1DIE\*LY-CvEMaiH iWi k Lit 2.4-Dichlorophenoxyacetic Acid (2,4-D) B. Impurity and By-product Formation (1) Sodium 2,6-dichlorophenoxyacetate (/ ^Vf-iOlH + ClCH2COONa 'ci NaOH 2,6-dichlorophenol (about 5% in 2,4-dichlorophenol) _ ^ C1 "Cl-+ V -OC^COONa + NaCl h 2o Sodium 2,6-dichlorophenoxyacetate (discarded in the mother liquor) JC1(2) Bis(2>4-dichlorophenoxy)acetic acid and sodium salt 2 C OH Cl2CH2COONa + 2NaOH e ) CHCOONa Sodium dichloroacetate (present in sodium monochloroacetate at 6%) Spdium bis(2,4-dichlorophenoxy)acetate (precipitates with Na 2,4-D) + 2NaCl + 2H20 Na2s4( c i ^ o ) 2.CHCOONa + H.2SO,4- -> 2 ( C I ^ O ) 2CHCOOH + Bis(2,4-dichlorophenoxy) acetic acid (3) Sodium glycolate ClCH2COONa + NaOH HOCH2COONa NaCl CONFIDENTI A Sodium glycolate (discarded in condensation re action mother liquor) i SUBJECT TO PROTECTIVE ORDER. 2- - HCG 11/21/83 C25062 A 8RHEY WGRX PRODUCT A n o e -c ira r e $ 2 ,4-Dichlorophenoxyacetic Acid(2,4-D) 4( ) Chlorinated dibenzo-ardioxins formed as impurities* The predominant chlorinated dioxins formed in the processes for 2,4-dichlorophenol and 2,4-D are as follows; (a) 2,7-DCDD DH Cl Cl Cl HO Cl heat Clbase .0. _ Gl '0 + 2HC1 2 ,4-dichlorophenol 2,7-dichlorodibenzo -p-dioxin (2,7-DCDD) Hydrogen chloride (b) 1,3,8-TCDD Cl Cl Cl HO XK OH Cl Cl 2,4-DCP 2,4,6-TCP 1,3,8-TCDD / (c) 1,3,6,8-and 1,3,7,9-TCDD Cl Cl ,C1 HO OH Cl Cl Cl heat base 2,4,6-TCP + 2HC1 Cl Cl SUBJECT TO PROTECTIVE ORDER, Cl No Cl 1,3,7,9-TCDD * References: (1) Persamon Ser. Environ. Sci. (PSSID2) Vol. 5, p. 209-213) (1982) C25063 (2) Journal of Chromatography. 217. 289-299 (1981) -3- HCG 11/21/83 P .. I -1/JP/r**V 2 ,4-Dichlorophenoxyacetic Acid(2,4-D) (d) 1,2,3,4,6,8-and 12,4,6,7,9- HCDD (Chemistry not clear) Cl 1,2,3,4,6,8-HCDD 1,2,4,6,7,9-HCDD Others are formed in lesser degree, but no 2,3,7,8-TCDD has been found. ATTORNEY WORK PRODUCT ATTO BIY-CUBIT PRWIiEE CONFIDENT! SUBJECT TO PROTECTIVE ORDER. -4- HCG 11/21/83 025064 CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. AATTTiOORRNKEEYY- CWLOIORiKT PPRRUiVDiULECrFE 2 ,4-Dichlorophenoxyacetic Acid(2,4-D) Chemicals Starting Materials 2,4-Dichlorophenol Sodium chloroacetate Sodium hydroxide Sulfuric acid Decolorizing carbon Sodium chloride (used in wash of Na 2,4-D) Structural Formula S rOH cl Cl ClCH2COONa WNaOH c NaCl Empirical Formual C6HAC12 C2H2C102Na HNaO H24s c NaCl CAS No. 120-83-2 3926-62-3 1310-73-2 7664-93-9 7440-44-0 7647-14-5 Isolated Intermediates Sodium 2,4-dichlorophenoxyacetate (Na 2,4-D) /-<C1 clV 7 " 0CH2C00Na By-products and Impurities of Toxicological Significance Sodium 2 ,6-dichlorophenoxyacetate Cl ^ _ n - O C H 2COONa " Sa-: Sodium bis(2,4-dichlorophenoxy)acetate ^ . ^ ^ ^ C O O N a CgH 5Cl203Na CgH 5Cl203Na C^Cl^Na 27Q2-72-9 No CAS No No CAS No C2&063 HCG 11/21/83 ATTORNEY-CIMI t t L Chemicals Bis(2,4-dichlorophenoxy) acetic acid 2,4-Dichlorophenoxyacetic Acid(2,4-D) Structural Formula (cH^o) CHCOOH Empirical Formula C14H 8C144 Sodium glycolate gto Oo o2 7o3 i gHl - w o Sodium 2 ,4-dichlorophenate (NaDCP) Known Chlorinated Dioxin Impurities 2,7-Dichlorodibenzo-p-dioxin (2,7-DCDD) " 1,3,6,8-Tetrachlorodibenzo-j)dioxin (1,3,6,8-TCDD) m> 1,3,7,9-Tetrachlorodibenzo-j^-dioxin (1,3,7,9-TCDD) H0CH2G00Na ONa Cl Cl- Cl Cl C2H 33Na C6H3C.12ONa C12H6 C1 2 2 C12H4C142 C12H4C142 CAS No. Mo CAS Mo. 2836-32-0 3757-76-4 33857-26-0 33423-926 62470-53-5 o 1,2,3,4,6,8-Hexachlorodibenzo-j>- O dioxin (1,2,3,4,6,8-HCDD) CN G G j C12H2 C1 62 58200-67-2 HCG 11/21/83 Chemicals 2 ,4-Dichlorophenoxyacetic Acid(2,4-D) Structural Formula Empirical Formula 1,2,4,6,7,9-Hexachlorodibenzo -p-dioxin (1,2,4,6,7,9-HCDD) C12H 2C162 1,3,8-Trichlorodibenzo-p-dioxin (1,3,8-TCDD) C12H 5C1302 D. Product 2 ,4-Dichlorophenaxyacetic acid (2 ,4-D) CI c l-C S OCH2 cooh W X23 GAS No, 39227-62-8 82306-61-4 94-75-7 ATTORNEY WORK PRODUCI m m -v m m m o to Cn I O 7 HCG 11/21/83 AITORm E j ,u{ PRODUCT ATTORNEY-CLIENT PRIVILEGE Asattlaldrcte-osunipgs,tnrtuhrcaettieoesnx.pwanodrkedwMasHcAoAmcpildetpeldanatpparpopxeiamrsatteolyboenpsrocdhuecdiunlge,MaHnAd,Acaifdter SANTO QUIN > yTSrpapepeelahqapranrnuerrtcteoio.rwqxetboutimmaiondteafcentrhtSteeeselasrysmniodtof9ioun0fq1eeSu3p,ai,ie3nfnrT,tcSomheaaqeninulrtptlieoinueosqrsinurcdaeeiubpnsneloietdaurunrnpeeeddcrcsooowpdvvaaeuenerrrcardeyty-.pvauvhanauBceirustnaiauesesgmedtadeivdfdirooinoninfsmget1s1ic4l91low07e2u1od.pl4udoSalutdtbaonentdbht1seore5efo$c.lJ2ef1o.x2vSwAF4eai.r,Wnt0ehQt0dou0fflereepoxnemyrAW oSedRnieaalmcnwowtoo'umaqnnsusatteitsrneraureticldeaocdlsesusisonessncafsuget,hleltfiyhsrsoeams$vuu5it0bnnh0sigettssietlxuooinptwfeieatednipradpflbiortesrouatxrSareiiarm.nntg-atuotoepqflu.yain$HL8aUu,sm0W0tbAh0leetphOleionriw-ly'fesierlamPbrreiaemarrveoianlpng3oo5wrl5uatbbomreriii,cnnawgenretar.>l1| TETRA CHLORO PRO PENE tofcboBchohuhneyiraitas-ndrncptggeoogorevoevnseddesuelteuirohpndtccpeepdethrmslrplmriaoeeeofbironadinilnrctn.eemttaoiaytetoLfhridinodaeeanblnfmdrca,ooloiremsenlascoovltthiosoanatroslvoeynuefeisawrbsiGtncmeioiLhsontr.uCltnkoetrsherrwHiiesnaataohrastsiweensatitaetborbpyvaenebrecgieotrhnour,tgglifntocertthehrtrmrooislicaoassphdfs.rriosewlonoappdIatryrnoesooaqnptpcuruersieonoicornpnpshileteruvelro,osnceocrcneloheettspaahssovrrseoere.fpuccrbelTheaenlsotaeoeapnnrlpodiyirnnssseweestvinoebttronlket 2 , 4 , 5-T Adscpimyurao$srupidt1rsneuo,tgm0icvc7teM.0tmchaoeacArlntacotpphrwwli,aatoaannu1lsdtl9dp6dndr9epeeo.meccjreeromTescnsahitst,asetrterthypaodetrtiotioohmsjneoempcdsrtpiaohueivpomnrerwctoaetev2ihndni,etd4tesThc,daC5aol-tePflToosarrinctocaoatfakhnuce2eeesw,ttrp4oitcarE,oib5inwdme-Tuaccwcs,ouhta.sw'csitmhaoaTksemphderiieonswwrvssqiaet,tasudhhlaltelhidtey CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 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CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 024771