ORGANIC PHOSPHORUS COMPOUNDS FOR INSECT PESTS CONTROL

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000700040419-1
• Release Decision: RIPPUB
• Original Classification: S
• Document Page Count: 4
• Document Creation Date: December 22, 2016
• Document Release Date: October 31, 2011
• Sequence Number: 419
• Publication Date: February 20, 1952
• Content Type: REPORT

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CLASSIFICATION _T SECT IL
Z'2C;K1 T T piiN'? Ip? J
CENTRAL IN tLUUC,! AG JGIY REPOR II
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS CD NO.
COUNTRY German Democratic Republic
SUBJECT Scientific - Chemistry, toxic substances
HOW
PUBLISHED Monthly periodical
WHERE
PUBLISHED Berlin
DATE
PUBLISHED Apr 1951
LANGUAGE German
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DATE OF
INFORMATION 1951
SUPPLEMENT TO
REPORT NO.
ORGANIC PHOSPHORUS COMPOUNDS FOR INSECT PESTS COiRTROL
This report giving data on phosphorus ccmpounds is an ixcerpt i'rom
a long article by Dr H. Fuerst (Magdeburg), "Progress in Pest Control
Chemistry," The remainder of the article contained generally known
data, based largely on material either published or available in the
US.
The Plant Protection Laboratory of the B-yer Dye Factories at Elberfeld has
been developing new insecticides since 1934. Most of this work was done by G.
Schrader.(1) These chemicals have become highly important for special pest-
control purposes. Thr^e groups of compounds were investigated, which became
important in the following chronological order:
a. Phosphoric Acid Esters of the Bladan type (TEPP end IIETP)
b. Thiophosphoric Acid Esters of the E 605 and E 838 type
c. Intratherapeutically active substances of the Pestox III type.
In the history of the development of the above compounds, Schrader describes
how he abandoned his original idea of synthesizing organic fluorine compounds to
make insecticides, and how he finally found the first powerful insecticide of the
phosphorus alkoxy series, 'he pyrophosphoric acid tetraethyl ester (TEPP):
C2H5D--,-11 ----OC2H5
P 0
-
C2H5O,
---OC2H5
a. A patent for this substance was taken out in 1938, but it did not become
known until 1945, when its discoverer was interrogated by FIAT of the US Army. (2)
Soon afterward, its production abroad was started and it was introduced there
under the name of TEPT. At the same time, work was done on hexaethyl tetraphosphate
(HETP), obtained by the older method from phosphorus oxychloride and triethyl phosphate:
4AYY N+RB
INAIR FBI
DISTRIBUTION
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I I I/ ?H5
POC13-) F=( - 0 - ~\ )3
2H5
By the more recent method, it is obtained directly from phosphorus oxy-
chloride and alcohol at 140?C. The yield is high; HC1 and ethyl chloride are
distilled off at reduced pressure.(3) The technical product is not homogeneous.
It is called Bladan.(4) It contains an ester mixture of the above general for-
mula. Up to 30 percent of it may be tetraethyl pyrophosphate, which is the ef-
fective component. If the substance contains less than 20 percent of this
compound, it is known as HETP; if the content is above 40 percent, it is called
TEPP.(5)
Bladan became known all over the world as an agent against plant lice
and caterpillars, equal to nicotine in effectiveness, and was used in 1:1000
aqueous solution. Due to the hydrolytic ester spliting the solution is unstable.
The toxicity of Bladan to warm-blooded annals equals that of nicotine. In
Germany, it has now been replaced by new products based on phosphoric acid esters,
such as E 605.
b. The new insecticide E 605 first became known abroad subsequent to inter-
rogation of Elberfe,d chemists after the war. After thorough research on phos-
phoric acid esters, they had succeeded in finding compounas which had higher
stability to water and alkalies than Bladan. Over the tetraethyl dithiopyrophos-
phates, which by themselves turned our to be useful, p-nitrophenyl diethyl phos-
phoric acid ester, called E 600, was obtained. It is also known by the name of
Mintacol:
V 2H5
P
\OC2H
It is too toxic to be used as an insecticide. However, it contracts
the pupils of the eyes and is therefore suitable as a pharmaceutical. Apparently,
combining of experiences gained with the hydrolysis-resistant dithiopbosphoric
acid ester and with E 600 led to the production of p-nitrophenyl diethyl thio-
phosphoric acid ester, called E 6u5c
J
02N-= -0 - p1/ Oc 2H5
\OC2115
Today, E 605 is made by the following method: Phosphorus trichloride
is quantitatively converted with sulfur to thiophosphorus trichloride. This is
then treated in an alcohol solution with the calculated quantity of sodium
ethylate, and the isolated intermediate product (diethoxy thiophosphoric acid)
is made to react with p-nitrophenol sodium.(6) er the solvent has been re-
moved, the crude product is obtained directly in the form of a yellow oil which
is insoluble in water.
The usual modifications of its constitution, i.e., substitution of other
alkyl groups, replacement of the -No2 group, etc., did not improve the effective-
ness of the substance.
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Foreign publications (7' also describe E 605 as e dimethyl thiophos-
phate of p-nitrophenol, while parathione is supposed to 1 diethyl thiophosphate.
E 605 resists hydrolysis and is thus sufficiently stable in aqueous spray
solutions. It is a contact, food, and respiration poison or pests. Its main
use as an insecticide is in the control of pests in orcha- _s and gardens, for
which nicotine, pyrethum, and lead ai enate were princip'lly used before. It is
supplied in different forms: as "E 605 forte" with 74 percent effective sub-
stance and 26 percent emulsifier (8); as "Folidol," an approximately 10 percent
oil concentrate; and as "E 605 dust." All these are toxic for warm-blooded
animals. A series with decreasing toxicity can be arranged as follows: Bladan,
E 605, Dieldrin, nicotine, Aldrin, Chlordane, DDT, gamma-HCH jamma-hexachloro-
cyclohexane7, pyrethrum.
A preparation similar to E 605 is manufactured in Western Germany under
the name "Pox" (T 47), made by Borchers Bros. of Goslar, and under the name of
"Wofatox" in the German Democratic Republic.(9) Abroad it is known as "Parathion"
or "Thiophos."
E 605 is not sufficiently effective against the potato bug. Only after
the war, in 1947, .+us a selective insecticide, E 838, developed to control this
pest. This substance, also kncwn as "Potasan," is the result of further system-
atic work on the E 605 series. It is the thiophosphoric acid ester of 4-methyl-
7-hydroxycoumarin. It was used on a large scale in 1950, is Loth a food and a
contact poison, according to the manufacturer's statements, and will also kill
the eggs of the bug. It is hard to tell just what prompted the people who devel-
oped this product to use the complex phenol 4-methyl-7-hydroxycoumarin. On the
other hand, Butenandt (10) in his work on the constitution of rotenone states
that one of its essential components is a coumarin nucleus. He also mentions
that two other substances of more simple structure, bergaptene and xanthotoxin,
which are coumarone-coumarins, resemble rotenone insecticide in their formula and
physiological properties.
C2H50~ 0 - co
~C2H50~ /Cx
E 838
CH3
C. The British systemic insecticide of the intratherapeutic type, Pestox
III (octamethylpyrophos)horic acid tetra-ami-_), while less poisonous than
E 605 or Bladan, is still strongly toxic to warm-blooded ani:nals.
BIBLIOGRAPHY
1.
Zeitschrift fuer angewandte Chemie, Vol 62, 1950,
p 441
2.
FIAT Final Report No 949, 14/10,
1949
3.
La Revue des Prod. Chim., Vol 50
Agriculture, Vol 14, 1950, p 115
(1.'
. p 181; L. Durand-Gasselin,
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5. S. A. Hall and M. Jacobson, Ind. Eng. Chem., Vol 40, 1948, p. 694
6. cf. 3
7. cf. 3
8. cf. 3
9. cf. 4
10. Rotenone, Annalen der Chemie, Vol 464, 1928, 1. 253.
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