Document ZJVjOYqQ16O2w743d891LZnx8
ATTORNEY WORK PRODUCT ATT1M Y - C I M PRlVUiGE
2.4-Dichlorophenoxyacetic Acid(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
Cl-^OH +
C1CH2COONa +
2 ,4-Dichlorophenol (produced at Kruiranrich by chlorination of phenol)
Sodium chloroacetate (Purchased from
Dow)
Step 2 - Acidification
NaOH 95 c
/ - < C1 'V-/ ~CH2COONa.
lis hrs.
Sodium 2,4-dichlorophenoxyacetate
(Na 2,4-D)
+ NaCl Sodium
chloride
+
h 20 Water
Cl
2
CH2COONa + H2S04
-- - C > 2cH ^ ^ - o c h 2C00H + Na,,SO. 24
15-30 min.
Sulfuric acid
2,4-D
Sodium sulfate
Step 3 - 2,4-Dichlorophenol Recovery
.Cl
2 ClL--(^_Vy-OtNa + H2S04
Sodium 2,4-dichlorophenate (present in condensa
tion reaction mother liquor)
-> 2Cl-^3-0H
Na2S04
2,4-dichlorophenol (recycled to conden
sation reaction)
CONFIDENTIAL
SUBJECT TO PROTECTIVE ORDER,
HCG 11/21/83 C25OJL
H IlH N E-CtlM A u
2,4-Dichlorophenoxyacetic Acid (2,4-D)
Impurity and By-product Formation (1) Sodium 2.6-dichlorophenoxyacetate
+ ClCH^COONa + NaOH
2,6-dichlorophenol (about 5% in 2,4-dichlorophenol)
CH^COONa + NaCl
+ H2
Sodium 2,6-dichlorophenoxyacetate (discarded In the
mother liquor)
(2) Bis(2,4-dichlorophenoxy)acetic acid and sodium salt
.Cl 2 OH
Cl2CH2COONa
2NaOH
W C1
.(c i-Q -o ) CHCOONa
Sodium dichloroacetate (present in sodium monochloroacetate at 6%)
Sodium bis(2,4r>dichlorO' phenoxy)acetate (precipitates with
Na 2,4-D)
2NaCl + 2H20
( c i - @ o ) CHCOONa
H2S04`
( * & ) ,,CHCOOH + Na.SO. 2 24
Bis(2,4-dichlorophenoxy) acetic acid
(3) Sodium glycolate
ClCHCOONa. +
NaOH ------- > HOCH2COONa + NaCl
Sodium glycolate (discarded in condensation re action mother liquor)
CONFIDENTI Ai,
SUBJECT TO PROTECTIVE ORDER.
-2-
HCG 11/21/83
C25062
ATTORTO WORK PRODUCT ATTORTO-G M P W !
2.4-Dichlorophenoxyacetic Acid(2,4-D)
(4) Chlorinated dibenzo-jrdioxlns 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 ODHH
jo C
Cl Cl
Cl '
xx
HO
heat base
Cl
0. _ Cl
TI
2HC1
2 ,4-dichlorophenol
2,7-dichlorodibenzo -p-dioxin 12,7-DCDD)
Hydrogen chloride
(b) 1,3,8-TCDD
Cl Cl
XX OH
HO 1
&
Cl Cl
+ 2HC1
2,4-DCP
2,4,6-TCP
1,3,8-TCDD
(c) 1,3,6,8-and 1,3,7,9-TCDD
C1 ^ ^ C1
X it 7 OH Cl
iCl
HO.
A
Cl Cl
heat base
2,4,6-TCP
2HC1
1,3,6,8-TCDD Smiles rearrangement
Cl Cl
SUBJECT TO PROTECTIVE ORDER.
-- V \ Cl ^0
1,3,7,9-TCDD
Cl
* References:
(1) Persamon Ser. Environ. Sci. (PSSID2) Vol. 5, p. 209-213) (1982)
C25063
(2) Journal of C h r o m a t o g r a p h y 289-299 (1981)
-3-
HCG 11/21/83
2,4-Dichlorophenoxyacetic Acld(2.4-D)
(d) 1,2,3,4,6,8-and 1.2,4,6,7,9- 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 ATTORNEY-CLIENT PRIVILEGE
CONFIDENTIAL
SUBJECT TO PROTECTIVE ORDER,
-4
HCG 11/21/83
C25064
ATTQRKEY WORK M i l l
ATTORNEY-CLIENT PiOVILL'E
2 ,4-Dichlorophenoxyacetic Acid(2 ,A-D)
CONFIDENTIAL
SUBJECT TO PROTECTIVE ORDER.
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
OH
<5r
Cl ClCH2COONa
NaOH
H2S04 c
NaCl
Empirical Formual
C6HAC12 C2H2C102Na
HNaO H2AS
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)
Cl C l - ^ ^ ~ O C H 2COONa
By-products and Impurities of Toxicological Significance
Sodium 2,6-dichlorophenoxyacetate
Sodium bis(2,4-dichlorophenoxy)acetate
r < C1 ^ _ V ~ O C H 2COONa
XI
)( c i ^ j y o CHCOONa
z
I
C8H 5C123Na C8H 5Cl203Na ^l^H/Cl^O^Na
2702-72-9
No CAS No No CAS No HCG 11/21/83
G25 06O
Chemicals
Bis(2,4-dichlorophenoxy) acetic acid
Allb<l liwiii a A h iw h -cum m m
2 ,4-Dichlorophenoxyacetic Acid(2,4-D)
Structural Formula
Empirical Formula
f >C1 ( C l - ^ y - 0 J CHC00H
C 14H 8C144
Sodium glycolate
Sodium 2 ,4-dichlorophenate (NaDCP)
H0CH2C00Na ONa
C2H303Na C,oH,,JC1,,LONa
CAS No. No CAS No 2836-32-0 3757-76-4
Known Chlorinated Dioxin Impurities
2,7-Dichlorodibenzo-p-dioxin (2,7-DCDD)
1,3,6,8-Tetrachlorodibenzo-dioxin (1,3,6,8-TCDD)
C12H6C122 C12H4C142
33857-26-0 33423-926
1,3,7,9-Tetrachlorodibenzo-jv-dioxin (1,3,7,9-TCDD)
o 1,2,3,A ,6 ,8-Hexachlorodibenzo-j)-
iO dioxin (1,2,3,4,6,8-HCDD) C*<
G2> Gj - 6 -
C12H4C142 C12H2C162
62470-53-5 58200-67-2 HCG 11/21/83
Chemicals
2 ,4-Dichlorophenoxyacetic Ac id(2,4-D)
Structural Formula
Empirical Formula
1,2,4,6,7,9-Hexachlorodibenzo -p-dioxin (1,2,4,6,7,9-HCDD)
C12H2C162
(ff n
ocaur?.
M
(<> -t
z
o
1,3,8-Trichlorodibenzo-p-dioxin (1,3,8-TCDD)
D. Product 2 ,4-Dichlorophenaxyacetic acid (2,4-D)
C12H 5C132 C8H6C123
CAS No. 39227-62-8 82306-61-4
94-75-7
ATfRHE 10 n C I
MTDRNEY-CUGT N W tE
O
co
Cr, i
O
OD
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HCG 11/21/83