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Pesticides
1. WHAT NEXT?
Thus far in our study of industrial chemistry we have covered in some
detail the top 100 chemicals produced as well as the important polymers
made by the chemical industry. We have especially studied their
manufacture and end uses, but have also looked at some history, economics,
and toxicological and environmental problems associated with some of these
products. In terms of net worth of shipments coming from these sectors, this
is over half of the chemical industry. What should we study next? Table
20.1 lists the U.S. shipments of the most important sectors of Chemical
Manufacturing along with other sectors of the chemical process industries.
If we add up the sectors already studiedBasic Chemicals; Resin, Synthetic
Rubber, and Artificial and Synthetic Fibers and Filaments; and Paints,
Coatings, and Adhesiveswe have 47% of Chemical Manufacturing. We
have also covered some of the chemistry associated with sectors outside
Chemical Manufacturing, such as Petroleum and Coal Products and Plastics
and Rubber Products, also big industries. We will now present in the
following chapters some specific selected technologies that will allow us to
learn about other important areas of the chemical industry. After we
complete our study of additional sectorsPesticides, Fertilizers, and Other
Agricultural Chemicals; Pharmaceuticals and Medicine; and Soap, Cleaning
Compounds, and Toilet Preparationswe will have increased our coverage
of Chemical Manufacturing to 91%. We have also included a chapter on
Paper Manufacturing, a fascinating industry with some interesting chemistry,
and one that employs many chemists.
Table 20.1 Shipments of Selected Sectors of Chemical Manufacturing
and Other Chemical Process Industries
2. INTRODUCTION TO PESTICIDES
Although pesticides have been criticized for many years as having many
side effects, it should be remembered that chemicals have been a prime
factor in agriculture's ability to keep pace with the hunger problem in the
world. Production of food crops would decrease by 30% without pesticides.
Production of livestock would drop 25%. Food prices would increase by 50-
75%. Because of pesticides, farmers can conserve wildland since they need
only half the land they used previously for the same amount of crops. Also,
pesticides have helped control many insect-borne diseases such as malaria,
yellow fever, encephalitis, and typhus. It is estimated that DDT alone (a bad
word nowadays) has saved 25,000,000 lives from sickness and famine and
has increased the lifespan in India by 15 years. Malaria is still a problem in
many of the world's countries, with a million per year dying of the disease.
Because of DDT's introduction during the 1940s, World War II was the first
war in which bullets killed more soldiers than insects. There is a definite
need to weigh carefully the benefits of technology on the one hand and the
risks in its application on the other.
Agricultural Chem.
Herbicides
Billions of Dollars
Insecticides
Year
Year
Figure 20.2 U.S. production of pesticides. (Source: Chemical and Engineering News,
"Facts and Figures for the Chemical Industry," and Chemical Economics Handbook)
branch. Herbicides passed them up in 1970 and have increased since then
while insecticides have decreased. Total production of insecticides today is
half of what it was in 1965, while herbicide use has increased four-fold since
1965. Table 20.2 gives the present production percentages of types of
pesticides, which are categorized by the type of pest that they attempt to
control. Other kinds are germicides, rodenticides, and miticides.
Agriculture uses about two thirds of all pesticides, with industrial,
commercial, home and garden, and government use dividing the other third.
Table 20.3 shows the percentage use of pesticides on various important
agricultural crops.
Herbicides 65%
Insecticides 14
Fungicides 10
Fumigants/Nematocides II
Source: Chemical Economics Handbook
Table 20.3 Uses of Pesticides on Crops
Corn 29%
Soybeans 19
Cotton 14
Deciduous Fruits/Nuts/Citrus 9
Other 29
Source: Chemical Economics Handbook
3. INSECTICIDES
3.1 History
nicotine pyrethrin I
rotenone
pyrethrins, originally obtained from Asian or Kenyan flowers, can now also
be synthesized laboriously. Nicotine is no longer used as an insecticide
because it is not safe for humans (smokers note).
As late as 1945 inorganic chemicals accounted for almost 75% of all
pesticide sales, with oil sprays and natural products being most of the
remainder. None of these first-generation insecticides are used much now.
During the 1950s the second generation of insecticides made an explosive
growth with the development of DDT and other chlorinated hydrocarbons.
Second-generation insecticides are of three major types: chlorinated
hydrocarbons, organophosphorus compounds, and carbamates. Synthetic
pyrethroids are a recent fourth type. Fig. 20.3 pictures the trend in
Organophosphates
Carbamates
Chlorinated Hydrocarb.
Millions of Pounds
Synth. Pyrethroids
Year
Oranophosphates 71%
Carbamates 20
Chlorinated hydrocarbons 3
Synthetic pyrethroids 2
Miscellaneous 4
Source: Chemical Economics Handbook
3.2.1 DDT
chloral chlorobenzene
DDT
Mechanism:
methoxychlor
3.2.2 Cyclodienes
cyclopentadiene
hexachlorocyclopentadiene chlordene
(HEX) (endo) free radical
substitution
ionic addition
dieldrin
(endo, exo)
(exo epoxide)
t1 /2 =6 yr
ispdrin
(endo, endo)
HEX + CH endrin
(endo, endo)
(exo epoxide)
t'/2=6yr
Much work has been done on the PCB problem. Potentially dangerous
amounts of PCBs have been found in fish. At the time of this writing the
EPA and General Electric are planning a $500 million cleanup of the
Hudson River sediment contaminated with PCBs even after many years of
being banned. A very toxic trace contaminant in European PCBs that may
be present in Monsanto's PCBs is tetrachlorodibenzofuran, the second most
toxic chemical known to humans.
tetrachlorodibenzofuran
The search for the ideal PCB replacement continues, especially for the
difficult electrical transformer application. Approximately 324 million Ib of
PCBs are still present in some 150,000 transformers. Possible substitutes
range from mineral oil to high-temperature hydrocarbons, with silicones by
far the most popular. There may be as much as a $2 billion market in
replacing PCB-containing transformers, which under 1985 EPA rules cannot
be used where they would present a contamination risk in human food or
animal feed.
TEPP
R = CH3CH2, parathion
diazinon
Table 20.5 U.S. Consumption of Organophosphates as Insecticides
Name Million Ib
Organophosphates, Total for 50 Compounds 93.3
Chlorpyrifos 18.5
Methyl parathion 14.0
Malathion 14.0
Terbufos 8.4
Phorate 5.5
Parathion 4.7
Source: Chemical Economics Handbook
physostigmine
carboftiran
A third important carbamate is aldicarb or Temik, an insecticide and
nematocide for potato and vegetable crops. This chemical has been found in
water wells in 11 states above the 1 ppm EPA safety threshold, barring use
in some locales in 1982. According to Union Carbide, one manufacturer,
humans can safely ingest 500 ppb. But it is one of the most acutely toxic
pesticides registered by the EPA. A fourth carbamate insecticide is
methomyl.
aldicarb
methomyl
Name Million Ib
Carbamates, Total for 13 Compounds 24.4
Carbaryl 8.0
Carbofuran 7.0
Aldicarb 3.9
Methomyl 3.2
Source: Chemical Economics Handbook
3.5 Synthetic Pyrethroids
Mention was made of the natural product pyrethrins and the structure of
pyrethrin I was given in this chapter, Section 3.1. Because of the unique
structures of these cyclopropane-containing natural products and their high
insecticidal properties, syntheses of analogs have been studied. The
isobutenyldimethylcyclopropanecarboxylic acid moiety, called chrysan-
themic acid, has been modified by using different ester groups. As a result a
number of synthetic pyrethroids are available for certain specific uses,
X Name
CH3 allethrin
CH3 dimethrin
CH3 resmethrin
Cl permethrin
Br decamethrin
multistriatin 4-methyl-3-heptanol
Year
4. HERBICIDES
The Department of Agriculture has estimated that about 10% of U.S.
agricultural products is lost because of weeds. About 1,500 species of weeds
cause economic loss. As we mentioned earlier, herbicide use rose
dramatically in the 1970s and 1990s, and herbicide consumption is now at
900 million Ib/yr with a worth of $6 billion/yr. In 1950 there were only 15
different herbicides; today there are over 180. Herbicides are used mainly
on corn, soybeans, wheat, and cotton.
Fig. 20.6 shows the trend in consumption for the three most important
types of herbicides. Carboxylic acids have been the standby for many years
and were the first type of herbicide. They were replaced as number one by
the heterocyclic nitrogen compounds in the 1970s. Carboxylic acids are
making a comeback in the 1990s. A close third are the amide herbicides.
The present percentage of consumption for herbicides is given in Table 20.7.
Table 20.7 Types of Herbicides
Rapid growth of chemical weed control did not occur until after World
War II when a herbicide was introduced by Jones in 1945 at the Imperial
Chemical Industries of England: 2,4-dichlorophenoxyacetic acid (2,4-D).
Its utility has come from its ability to kill selectively broadleaf weeds in
cereal grains, corn, and cotton. It does not disturb the soil and is not
persistent. 2,4,5-T was launched commercially by American Chemical Paint
Co. in 1948 (now Union Carbide) to combat brush and weeds in forests,
along highways and railroad tracks, in pastures, and on rice, wheat, and
sugarcane.
2,4-Dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic
acid (2,4,5-T) dominated the herbicide market up to the late 1960s. These
are sometimes called phenoxy herbicides. Phenol is the starting material for
2,4-D. Chlorination via electrophilic aromatic substitution (know the
mechanism!) gives 2,4-dichlorophenol. The sodium salt of this compound
can react with sodium chloroacetate (SN2) and acidification gives 2,4-D.
2,4,5-T can be synthesized easily. Chlorination of benzene gives 1,2,4,5-
tetrachlorobenzene (why this isomer?) which reacts with caustic to give
2,4,5-trichlorophenol. A conversion similar to the preceding one yields the
phenoxyacetic acid 2,4,5-T.
TCDD
silvex
dicamba
glycine
glyphosate
4.2 Heterocyclic Nitrogen Herbicides
The most widely used herbicides today are triazine compounds (three
nitrogens in the heterocyclic aromatic ring). Atrazine is used especially on
corn but also on pineapple and sugarcane. It is synthesized by reacting
cyanuryl chloride successively with one equivalent of ethylamine and one
equivalent of isopropylamine. Cyanuryl chloride is made in one step from
cyanuryl chloride
atrazine
cyanazine bentazon
4.3 Amide Herbicides
propanil
4.4 Dinitroanilines
pendimethalin benefin
4.5 Summary
Table 20.8 lists the herbicides discussed here with their annual U.S.
Name Million Ib
Heterocyclic Nitrogens, total 163.2
Atrazine 73.0
Cyanazine 20.0
Bentazon 8.0
Carboxylic Acids, total 130.0
Glyphosate 40.0
2,4-D 30.0
Dicamba 10.0
Amides, total 118.4
Metolachlor 63.0
Acetochlor 30.0
Alachlor 16.0
Propanil 7.0
Dinitroanilines, total 62.0
Pendimethalin 24.0
Trifluralin 23.0
Source: Chemical Economics Handbook
consumption, together with the total for each major type of herbicide. In this
chapter we have taken up our first example of a sector of the chemical
industry that involves multistep organic syntheses, very diverse organic
chemical structures, and final compounds which are unique in their
biological action and selectivity. We will see this type of industrial sector
again when we study the pharmaceutical industry in Chapter 23. Despite
this complexity of chemistry most of the major pesticides fall into one
chemical class or another that has been shown to give the desired biological
response. Then slight modifications of structures are used for specific
applications to maximize the desired effect and minimize the side effects. In
summary, the insecticide market is now dominated by the organophosphates
and the carbamates. The herbicide market is a little more diverse, but
heterocyclic nitrogens, carboxylic acids, amides, and dinitroanilines are the
main materials.
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