Cursuri Antid 8-13 Final

Cyclodiene organochlorine
insecticides
▪ However, the Diels-Alder cycloaddition of
hexachlorocyclopentadiene with norbornadiene gives
practically only aldrin. The kinetically preferred transition
state involves approach of the hexachlorocyclopentadiene
upon the exo face of one of the two equivalent double bonds
in the dienophile (exo facial stereoselectivity). From the two
possible exo transition states the one that minimizes the steric
interaction between a C(5)-Cl bond in the diene and the anti
C(7)-H bond in the dienophile (108) is preferred leading to
aldrin.
1
insecticides
2
insecticides
▪ By contrary, isodrin is formed through a kinetically preferred
transition state involving the approach of the diene
(cyclopentadiene) upon the endo face of the non-chlorinated
double bond in the hexachloronorbornadiene dienophile.
From the two possible endo transition states (113 and 114),
the one that leads to the formation of isodrin (114) minimizes
non-bonded steric interactions between a C(5)-H bond in the
diene and the dienophile.
3
insecticides
4
Cyclodiene organochlorine insecticides
A. Nestorovska-Krsteska,Z. Zdravkovski. Theoretical study of the diastereofacial
isomers of aldrin and dieldrin. Int. J. Mol. Sci., 2006, 7, pp. 35-46.
A.P. Marchand, B. Ganguly, C.I. Malagón, H. Lai, W. Watson. Experimental and
theoretical studies of Diels-Alder dimerization of 1,2,3,4,5-
pentachloropentadiene and of Diels-Alder cycloaddition of polychlorinated
cyclopentadienes to norbornadiene. Tetrahedron, 2003, 59, pp. 1763-1771.
P.H. Mazzocchi, B. Stahly, J. Dodd, N.G. Rondan, L.N. Domelsmith, M.D. Rozeboom,
P. Carmella, K.N. Houk. π-Facial stereoselectivity: Rates and stereoselectivities of
cycloadditions of hexachlorocyclopentadiene to 7-substituted norbornadienes,
and photoelectron spectral and molecular orbital computational investigations of
norbornadienes. J. Am. Chem. Soc., 1980, 102 (21), pp 6482–6490.
A.P. Marchand, H.S. Chong, B. Ganguly, J.M. Coxon, π-Facial selectivity in Diels-
Alder cycloadditions. Croat. Chem. Acta, 2000, 73, pp. 1027-1038.
5
insecticides
▪ Polycyclic compounds
Mirex (115) and kepone (117). Mirex is obtained from
hexachlorocyclopentadiene on treatment with aluminum chloride
in methylene chloride or carbon tetrachloride. In another synthetic
route hexachlorocyclopentadiene undergoes first Diels-Alder
cyclodimerization to the corresponding
dodecachlorodicyclopentadiene 116 which in the presence of
aluminum chloride or antimony chloride isomerizes to mirex.
Kepone is formed by heating hexachlorocyclopentadiene at 35-
80°C with chlorosulfonic acid, fuming sulfuric acid or sulfur
trioxide.
6
Cyclodiene organochlorine insecticides
7
Organophosphorus insecticides
8
Fundamental reactions of
organophosphorus chemistry
9
10
11
12
13
14
15
16
Phosphoric acid derivatives
with insecticidal activity
1. Phosphoric acid diamide fluorides
1
Phosphoric acid derivatives with
insecticidal activity
2. Phosphoric acid esters.
Substituted dialkyl-phenyl phosphates
2
Dialkyl enol phosphates
Dichlorvos (see slide 129) can be obtained either from trimethyl
phosphite by a Perkow reaction with chloral (see slide 126) or
from dimethyl phosphonate via the intermediacy of
trichlorfon the latter being converted to dichlorvos through
elimination of hydrochloric acid under basic consitions (see
slide 129) .
3
3. Ester amides of phosphoric acid.
Phospholan
4
Thiophosphoric acid
derivatives with
1. Substituted dialkyl-phenyl phosphorothioates
5
Thiophosphoric acid derivatives
John Michniak, Process

for the production of 2,5-
dichloro-4-bromophenol.
US Patent 4,067,913, Jan.
10, 1978
6
Ebenezer Jones-Mensah, Megha Karki, Jakob Magolan,

Dimethyl Sulfoxide as a Synthon in Organic Chemistry, Georg Thieme Verlag Stuttgart
New York — Synthesis 2016, 48, A–P
7
Thiophosphoric acid derivatives with
8
Thiophosphoric acid
derivatives with
2. Phosphorothioates containing alkylthioalkyl
groups.
Demeton (Systox®)
9
Thiophosphoric acid
derivatives with
10
Thiophosphoric acid
derivatives with
Systox thion-thiol isomerisation.
11
Thiophosphoric acid
derivatives with
Syntheses of the thion form.
12
Thiophosphoric acid
derivatives with
Syntheses of the thiol form.
13
Thiophosphoric acid
derivatives with
Syntheses of the thiol form.
14
Thiophosphoric acid
derivatives with
3. Ester amides of thiophosphoric acid
(phosphoroamidothioates).
Methamidophos and acephate.
Dimethyl phosphorothiochloridate can easily be
converted with ammonia to O,O-dimetyl
phosphorothioamidate which, in the presence of
a methylating agent like dimethyl sulfate,
undergoes thion→thiol isomerisation, and it’s
converted to the O,S-dimethyl analogue
(methamidophos) which in turn can be acylated
with acetic anhydride to eventually give
acephate.
1
Thiophosphoric acid
derivatives with
2
Thiophosphoric acid
derivatives with
4. Oxime thiophosphates.
Phoxim
3
Thiophosphoric acid
derivatives with
5. Dialkyl-heteroaryl phosphorothioates.
Chlorpyrifos
4
Thiophosphoric acid
derivatives with
R. Garth Pews, Process for the preparation of 3,5,6-

trichloropyridin-2-ol, United States Patent, 4,996,323, Feb.
26, 1991. 5
Pyraclofos
6
7
A better variant suitable for industrial
application
Yoshiyuki Okada, Yasuo

Sato, 1-PHENYL-4-
HYDROXYPYRAZOLE
DERIVATIVES, United States
Patent, 4,621,144, Nov. 4,
1986.
8
Thomas A. Unger, Pesticide Synthesis Handbook,

Noyes Publications, 1996, ISBN: 0-8155-1401-8.
9
Yoshiyuki Okada, Yoshihiro

Inoue, Koichi Iwanaga,
PYRAZOL-4-YL PHOSPHITES,
United States Patent,
4,531,005, Jul. 23, 1985
10
Dithiophosphoric acid
derivatives with insecticidal
activity
1. Phosphorodithioates containing amide
groups.
11
derivatives with insecticidal
activity
2. Phosphorodithioates containing carboxylic
acid ester groups.
Malathion
12
derivatives with
3. Phosphorodithioates containing
alkylthioalkyl groups.
Phorate
13
Carbamate insecticides
1
▪ Carbamoyl chlorides
▪ Carbamates
From carbamoyl chlorides and alcohols
2
▪ Carbamates
From chloroformates (prepared from phosgene
and alcohols) and amines
From isocyanates (prepared from monosubstituted

carbamoyl chlorides) and alcohols
3
▪ Carbamates
From carbonates (prepared from alkoxides and phosgene) and
amines
4
▪ N,N-dimethylcarbamates
Dimetan
5
Isolan
6
Pirimicarb
7
▪ N-methylcarbamates
Carbaryl
8
Metolcarb
9
Promecarb
Alfons Klein, Karlfried Wedemeyer, PROCESS FOR THE PREPARATION OF

5-ISOPROPYL-3-METHYL-PHENOL, US Patent, 3,968,173, July 6,1976.
Gerd Leston, PREPARATION OF 5-SEC-ALKYL-M-CRESOL, US Patent, 3,992,455,
Nov. 16, 1976.
10
Carbamolate
11
Mexacarbate
12
Carbofuran and Carbosulfan
13
▪ Oxime carbamates
Methomyl
14
▪ Joseph T. Blackwell, PROCESS FOR THE PRODUCTION OF

METHOMYL OXIME, US Patent, 4,327,033, Apr. 27, 1982.
▪ Zohar Oren, PROCESS FOR THE PRODUCTION OF
METHOMYL OXIME, US Patent, 4,683,322, Jul. 28, 1987.
15
Aldicarb
Alternate route:
1
Oxamyl
2
▪ Joseph J. Mrowca, PROCESS FOR PREPARING METHYLCARBAMATE
INSECTICIDES, US Patent, 4,668,806, May 26, 1987.
▪ James B. Buchanan, SUBSTITUTED O-CARBAMYLHYDROXAMATES, US
Patent, 3,576,834, Apr. 27, 1971.
▪ James B. Buchanan, ALKYL l-CARBAMOYL-N-(SUBSTITUTED-
CARBAMOYLOXY)THIOFORMIMIDATES, US Patent, 3,658,870, Apr. 25, 1972.
▪ Linwood K. Payne, Jr., Charleston, W. Va., and Mathias H. J. Weiden, 2-
HYDROCARBYLTHIO-SULFINYL AND SULFONYLALKANAL
CARBAMOYLOXIMES, US Patent, 3,217,113 7, Nov. 9, 1965.
▪ William G. Scharpf, 2,2-DIMETHYL-2,3-DIHYDROBENZOFURANYL 7-N-
METHYLCARBAMATE, US Patent, 3,474,171, Oct. 21, 1969.
▪ Joseph A. Lambrech, α-NAPHTHOLBICYCLIC A'RYL ESTERS OF N –
SUBSTITUTED CARBAMIC ACIDS, US Patent 2,993,478, Sept. 8, 1959.
▪ Vagab S. Aliev, Sakhib M. O. Aliev, Farrukh R. O. Gadzhiev, Novruz I. O. Guseinov,
Shamkhal A. M. O. Mamedov, Medzhid A. Mardanov, Rafail S. Sverdlov, Dzhavid
N. O. Khydyrov, PROCESS FOR PREPARING METHYL ISOCYANATE, US Patent,
4,255,350, Mar. 10, 1981.
▪ Günter Giesselmann, Kurt Günther, Werner aus der Fünten, PROCESS FOR THE
PRODUCTION OF METHYLISOCYANATE , US Patent, 4,206,136, Jun. 3, 1980.
3
General structure of neonicotinoid
insecticides
4
Imidacloprid
▪ Synthesis of the heterocyclic group
5
Imidacloprid
▪ Chemical synthesis of 6-hydroxy nicotinic acid
6
Imidacloprid
7
Imidacloprid
▪ Enzymatic (green) synthesis of 6-hydroxy

nicotinic acid
8
Imidacloprid
▪ Synthesis of the toxicophore
9
Imidacloprid
10
Imidacloprid
▪ Synthesis of the neonicotinoid insecticide
11
Imidacloprid
▪ Synthesis of the neonicotinoid insecticide (a
better variant)
12
Clothianidin
13
Clothianidin
14
Clothianidin
15
Clothianidin
very poor yield
16
Clothianidin
Therefore,
17
Clothianidin
18
Thiacloprid
1
Thiacloprid
▪ Another variant
2
Thiacloprid
3
Thiamethoxam
▪ Synthesis
▪ Conversion of thiamethoxam into clothianidin
4
Thiamethoxam
▪ An improved synthesis of clothianidin
5
Dinotefuran
6
Dinotefuran
7
HERBICIDES
1. Imidazolinone herbicides.
Imazaquine.
Synthesis.
8
HERBICIDES
▪ Mechanism of the Vilsmeier formylation
reaction.
9
HERBICIDES
Synthesis of 2-amino-2,3-dimethylbutanenitrile.
Imazethapyr.
Synthesis. First method.
10
HERBICIDES
▪ Synthesis of 5-ethylpyridine-2,3-dicarboxylic acid.
▪ Mechanism
11
HERBICIDES
▪ Synthesis of imazethapyr. Second method.
12
HERBICIDES
▪ Synthesis of imazethapyr. Third method.
▪ Synthesis of ethyl 5-ethyl-2-methylnicotinate.
▪ Mechanism of the Willgerodt reaction.
13
HERBICIDES
2. Cyclohexane dione herbicides.
Clethodim.
Synthesis.
14
HERBICIDES
Synthesis of O-(3-chloroallyl)hydroxylamine.
15
HERBICIDES
3. Aryloxyphenoxypropionate herbicides.
Diclofop-methyl.
Synthesis.
16

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Cyclodiene organochlorine

John Michniak, Process

Ebenezer Jones-Mensah, Megha Karki, Jakob Magolan,

R. Garth Pews, Process for the preparation of 3,5,6-

Yoshiyuki Okada, Yasuo

Thomas A. Unger, Pesticide Synthesis Handbook,

Yoshiyuki Okada, Yoshihiro

From isocyanates (prepared from monosubstituted

Alfons Klein, Karlfried Wedemeyer, PROCESS FOR THE PREPARATION OF

▪ Joseph T. Blackwell, PROCESS FOR THE PRODUCTION OF

▪ Enzymatic (green) synthesis of 6-hydroxy

▪ Synthesis of the neonicotinoid insecticide

▪ Synthesis of the heterocyclic group

▪ Synthesis of the toxicophore

▪ Synthesis of the neonicotinoid insecticide

very poor yield

▪ Synthesis of the toxicophore

▪ Synthesis of the neonicotinoid insecticide

▪ Conversion of thiamethoxam into clothianidin

▪ Synthesis of the neonicotinoid insecticide

Synthesis. First method.

▪ Synthesis of imazethapyr. Second method.

▪ Synthesis of ethyl 5-ethyl-2-methylnicotinate.

▪ Mechanism of the Willgerodt reaction.

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