carbamate insecticide

• カルバメート系殺虫剤

WordNet

1. a chemical used to kill insects (同)insect_powder
2. a salt (or ester) of carbamic acid

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1. 殺虫剤

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/09/27 15:04:13」(JST)

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Chemical structure of carbamates

A carbamate is an organic compound derived from carbamic acid (NH₂COOH). A carbamate group, carbamate ester (e.g., ethyl carbamate), and carbamic acids are functional groups that are inter-related structurally and often are interconverted chemically. Carbamate esters are also called urethanes.

Synthesis

Carbamic acids are derived from amines:

R₂NH + CO₂ → R₂NCO₂H

Carbamic acid is about as acidic as acetic acid. Ionization of a proton gives the carbamate anion, the conjugate base of carbamic acid:

R₂NCO₂H → R₂NCO₂⁻ + H⁺

Carbamates also arise via hydrolysis of chloroformamides and subsequent esterification:

R₂NC(O)Cl + H₂O → R₂NCO₂H + HCl

Carbamates may be formed from the Curtius Rearrangement, where isocyanates formed are reacted with an alcohol.

RNCO + R'OH → RNHCO₂R'

Applications and occurrence

Although most of this article concerns organic carbamates, the inorganic salt ammonium carbamate is produced on a large scale as an intermediate in the production of the commodity chemical urea from ammonia and carbon dioxide.

Carbamates in biochemistry

N-terminal amino groups of valine residues in the α- and β-chains of deoxyhemoglobin exist as carbamates. They help to stabilise the protein, when it becomes deoxyhemoglobin and increases the likelihood of the release of remaining oxygen molecules bound to the protein. This stabilizing effect should not be confused with the Bohr Effect (an indirect effect caused by carbon dioxide).

The ε-amino groups of the lysine residues in urease and phosphotriesterase also feature carbamate. The carbamate derived from aminoimidazole is an intermediate in the biosynthesis of inosine. Carbamoyl phosphate is generated from carboxyphosphate rather than CO₂.

CO₂ capture by ribulose 1,5-bisphosphate carboxylase

Perhaps the most important carbamate is the one involved in the capture of CO₂ by plants since this process is necessary for their growth. The enzyme ribulose 1,5-bisphosphate carboxylase/oxygenase fixes a molecule of carbon dioxide as phosphoglycerate in the Calvin cycle. At the active site of the enzyme, a Mg²⁺ ion is bound to glutamate and aspartate residues as well as a lysine carbamate. The carbamate is formed when an uncharged lysine side-chain near the ion reacts with a carbon dioxide molecule from the air (not the substrate carbon dioxide molecule), which then renders it charged, and, therefore, able to bind the Mg²⁺ ion.

Commercial carbamate compounds

Carbamate insecticides

The carbamate insecticide Carbaryl.

The so-called carbamate insecticides feature the carbamate ester functional group. Included in this group are aldicarb (Temik), carbofuran (Furadan), carbaryl (Sevin), ethienocarb, fenobucarb, oxamyl and methomyl. These insecticides kill insects by reversibly inactivating the enzyme acetylcholinesterase. The organophosphate pesticides also inhibit this enzyme, although irreversibly, and cause a more severe form of cholinergic poisoning.

Fenoxycarb has a carbamate group but acts as a juvenile hormone mimic, rather than inactivating acetylcholinesterase.

The insect repellent icaridin is a substituted carbamate.

Polyurethanes

Main article: Polyurethane

Polyurethanes contain multiple carbamate groups as part of their structure. The "urethane" in the name "polyurethane" refers to these carbamate groups; the term "urethane links" describe how carbamates polymerize. In contrast, the substance commonly called "urethane," ethyl carbamate, is neither a component of polyurethanes, nor is it used in their manufacture. Urethanes are usually formed by reaction of an alcohol with an isocyanate. Commonly, urethanes made by a nonisocyanate route are called carbamates.

Polyurethane polymers have a wide range of properties and are commercially available as foams, elastomers, and solids. Typically, polyurethane polymers are made by combining diisocyanates, e.g. toluene diisocyanate, and diols, where the carbamate groups are formed by reaction of the alcohols with the isocyanates:

RN=C=O + R'OH → RNHC(O)OR'

Preservatives and cosmetics

Iodopropynyl butylcarbamate is a wood and paint preservative and used in cosmetics.

In human medicine

Urethane (ethyl carbamate) was once produced commercially in the United States as an antineoplastic agent and for other medicinal purposes. It was found to be toxic and largely ineffective. It is occasionally used as a veterinary medicine.

In addition, some carbamates are used in human pharmacotherapy, for example, the cholinesterase inhibitors neostigmine and rivastigmine, whose chemical structure is based on the natural alkaloid physostigmine. Other examples are meprobamate and its derivatives like carisoprodol, felbamate, mebutamate and tybamate, a class of anxiolytic and muscle relaxant drugs widely used in the 60s before the rise of benzodiazepines, and still used nowadays in some cases.

The protease inhibitor darunavir for HIV treatment also contains a carbamate functional group.

Sulfur analogues

There are two oxygen atoms in a carbamate (1), ROC(=O)NR₂, and either or both of them can be conceptually replaced by sulfur. Analogues of carbamates with only one of the oxygens replaced by sulfur are called thiocarbamates (2 and 3). Carbamates with both oxygens replaced by sulfur are called dithiocarbamates (4), RSC(=S)NR₂.

There are two different structurally isomeric types of thiocarbamate:

• O-thiocarbamates (2), ROC(=S)NR₂, where the carbonyl group (C=O) is replaced with a thiocarbonyl group (C=S)
• S-thiocarbamates (3), RSC(=O)NR₂, where the R–O– group is replaced with an R–S– group

O-thiocarbamates can isomerise to S-thiocarbamates, for example in the Newman-Kwart rearrangement.

See also

• Methyl carbamate
• Ethyl carbamate
• Polyurethane

References

UpToDate Contents

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• 1. 有機リン剤およびカルバメート中毒 organophosphate and carbamate poisoning
• 2. 神経筋接合部に作用する毒素の概要 overview of neuromuscular junction toxins
• 3. 殺鼠剤中毒の概要 overview of rodenticide poisoning
• 4. 流行地域におけるマラリアの疫学、予防、および管理 epidemiology prevention and control of malaria in endemic areas
• 5. アレルギー性接触皮膚炎の一般的なアレルゲン common allergens in allergic contact dermatitis

English Journal

• Comparative toxicity of carbaryl, carbofuran, cypermethrin and fenvalerate in Metaphire posthuma and Eisenia fetida -A possible mechanism.

• Saxena PN1, Gupta SK1, Murthy RC2.Author information 1Cell Biology Division CSIR-Indian Institute of Toxicology Research, Lucknow 226001, India.2Cell Biology Division CSIR-Indian Institute of Toxicology Research, Lucknow 226001, India. Electronic address: murthyrc@rediffmail.com.AbstractTo establish the use of Metaphire posthuma as a sensitive test model for ecotoxicological studies, acute toxicity testing of carbaryl, carbofuran, cypermethrin and fenvalerate on Eisenia fetida and Metaphire posthuma were carried out. Two different types of bioassays, contact filter paper toxicity and soil toxicity bioassays were used to determine LC50 values for these insecticides. Among the tested chemicals, carbofuran was the most toxic to both the earthworm species. In paper contact method, 72h-LC50 values of carbofuran in M. posthuma and E. fetida were found to be 0.08μg/cm(2) and 1.55μg/cm(2) respectively while in soil test, 14-d LC50 values were 0.49mg/kg and 21.15mg/kg respectively. On comparing the toxicity data of these chemicals for both the earthworm species, M. posthuma was found to be more sensitive than E. fetida. Based on the acute toxicity data, the order of toxicity of insecticides in both the test procedures was carbofuran>cypermethrin>carbaryl>fenvalerate for M. posthuma whereas for E. fetida it was carbofuran>carbaryl>fenvalerate>cypermethrin. Morphological changes also appeared in the organisms exposed to these chemicals which were more pronounced in M. posthuma at lower concentrations than E. fetida in both the test procedures. The results of the present study advocates the use of M. posthuma for ecotoxicity studies, being a more sensitive and reliable model than E. fetida. Based on the data on partial atomic charges, structural features and spectroscopic studies on carbaryl and carbofuran, a possible mechanism of toxicity of carbamate insecticides in earthworm was proposed.
• Ecotoxicology and environmental safety.Ecotoxicol Environ Saf.2014 Feb;100:218-25. doi: 10.1016/j.ecoenv.2013.11.006. Epub 2013 Dec 7.
• To establish the use of Metaphire posthuma as a sensitive test model for ecotoxicological studies, acute toxicity testing of carbaryl, carbofuran, cypermethrin and fenvalerate on Eisenia fetida and Metaphire posthuma were carried out. Two different types of bioassays, contact filter paper toxicity a
• PMID 24321850

• Modulatory effects of deltamethrin-exposure on the immune status, metabolism and oxidative stress in gilthead seabream (Sparus aurata L.).

• Guardiola FA1, Gónzalez-Párraga P1, Meseguer J1, Cuesta A1, Esteban MA2.Author information 1Fish Innate Immune System Group, Department of Cell Biology and Histology, Faculty of Biology, Campus Regional de Excelencia Internacional "Campus Mare Nostrum", University of Murcia, 30100 Murcia, Spain.2Fish Innate Immune System Group, Department of Cell Biology and Histology, Faculty of Biology, Campus Regional de Excelencia Internacional "Campus Mare Nostrum", University of Murcia, 30100 Murcia, Spain. Electronic address: aesteban@um.es.AbstractDeltamethrin, a sintetic pyrethroid, is the insecticide that has been replacing recently to others like organochlorines, organophosphates and carbamates which are less toxic for birds and mammals, although, unfortunately, all of them are highly toxic to various non-targeted aquatic organisms including fish. In the present study, the consequences of the exposition of gilthead seabream (Sparus aurata L.) specimens to sublethal bath dose of deltamethrin (0.1 ppb) on organo-somatic indexes, immunity, seric metabolic parameters, oxidative stress and liver histology were determined after 1, 3, 7 and 14 days of exposure. Deltamethrin alters gilthead seabream immune status, the hepato-somatic index and various seric metabolic parameters since the first exposure day while important progressive deleterious morphological changes in liver were also observed. However, no statistically significant deviation was detected in the expression of oxidative stress-related genes whilst the expression of cytochrome P450 gene was up-regulated in head-kidney and liver of exposed fish. Overall, the present results indicate severe immunotoxicological and metabolic effects of deltamethrin in gilthead seabream, the species with the highest rate of production in Mediterranean aquaculture. In general, the values obtained for the tested parameters during the trial seem to indicate that specimens try to adapt to this adverse situation although the continuous presence of the toxic impede the hypothetic recovery of homoeostasis. The use of deltamethrin in the proximities of seabream farms should be carefully considered.
• Fish & shellfish immunology.Fish Shellfish Immunol.2014 Jan;36(1):120-9. doi: 10.1016/j.fsi.2013.10.020. Epub 2013 Oct 29.
• Deltamethrin, a sintetic pyrethroid, is the insecticide that has been replacing recently to others like organochlorines, organophosphates and carbamates which are less toxic for birds and mammals, although, unfortunately, all of them are highly toxic to various non-targeted aquatic organisms includi
• PMID 24176818

• The combined toxicity assessment of carp (Cyprinus carpio) acetylcholinesterase activity by binary mixtures of chlorpyrifos and four other insecticides.

• Chen C, Wang Y, Zhao X, Wang Q, Qian Y.Author information Key Laboratory of Agro-Product Quality and Safety of Ministry of Agriculture, Institute of Quality Standards and Testing Technology for Agro-Products, Chinese Academy of Agricultural Sciences, Beijing, 100081, China.AbstractMixtures of organophosphate (OP) and carbamate (CB) insecticides are commonly detected in freshwater habitats. These insecticides inhibit the activity of acetylcholinesterase (AChE) and have potential to interfere with behaviors that may be essential for survival of species. Although the effects of individual anticholinesterase insecticides on aquatic species have been studied for decades, the combined toxicity of mixtures is still poorly understood. In the present study, we assessed whether pesticides in a mixture act in isolation (resulting in additive AChE inhibition) or whether components interact to produce either antagonistic or synergistic toxicity. Brain AChE inhibition in carp (Cyprinus carpio L.) exposed to a series of concentrations of the OP (chlorpyrifos, malathion and triazophos) as well as the CB (fenobucarb and carbosulfan) were measured. The concentration addition (CA) model and the isobole method were used to determine whether toxicological responses to binary mixtures of pesticides. In 50:50 % effect mixtures, the observed combined toxicity of chlorpyrifos and malathion was significantly higher than observed and was considered as synergistic. For equivalent dose mixtures, when chlorpyrifos mixed with fenobucarb or malathion, the observed toxicities were significantly higher than predicted, suggesting synergistic joint actions. The rest five binary combinations exhibited concentration additive or slight antagonistic joint actions. The CA model and the isobole method provided estimates of mixture toxicity that did not markedly underestimate the measured toxicity, therefore these methods are suitable to use in ecological risk assessments of pesticide mixtures.
• Ecotoxicology (London, England).Ecotoxicology.2013 Dec 23. [Epub ahead of print]
• Mixtures of organophosphate (OP) and carbamate (CB) insecticides are commonly detected in freshwater habitats. These insecticides inhibit the activity of acetylcholinesterase (AChE) and have potential to interfere with behaviors that may be essential for survival of species. Although the effects of
• PMID 24363216

Japanese Journal

• コイ血漿メタボロミクスによるカーバメート系殺虫剤BPMCの有害性評価

• 國師 恵美子,宇野 誠一,小山 次朗
• 環境毒性学会誌 16(1), 1-11, 2013-06
• NAID 40019782388

• 輸入農産物中の残留農薬実態調査(有機塩素系農薬, N-メチルカルバメート系農薬及びその他) : 平成23年度

• 八巻 ゆみこ,小林 麻紀,大塚 健治 [他]
• 東京都健康安全研究センター研究年報 (63), 221-227, 2012
• NAID 40019810757

• 輸入農産物中の残留農薬実態調査(有機塩素系農薬,N-メチルカルバメート系農薬及びその他) : 平成22年度

• 木下 輝昭,小林 麻紀,大塚 健治 [他]
• 東京都健康安全研究センター研究年報 -(62), 191-197, 2011
• NAID 40019236245

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