Nereistoxin

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Nereistoxin
Nereistoxin.svg
Names
Preferred IUPAC name
N,N-Dimethyl-1,2-dithiolan-4-amine
Other names
NTX
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.121.136 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • Cartap:239-309-2
KEGG
PubChem CID
UNII
  • Nereistoxin:InChI=1S/C5H11NS2/c1-6(2)5-3-7-8-4-5/h5H,3-4H2,1-2H3
    Key: DSOOGBGKEWZRIH-UHFFFAOYSA-N
  • Cartap:InChI=1S/C7H15N3O2S2/c1-10(2)5(3-13-6(8)11)4-14-7(9)12/h5H,3-4H2,1-2H3,(H2,8,11)(H2,9,12)
    Key: IRUJZVNXZWPBMU-UHFFFAOYSA-N
  • Bensultap:Key: YFXPPSKYMBTNAV-UHFFFAOYSA-N
  • Nereistoxin:CN(C)C1CSSC1
  • Cartap:CN(C)C(CSC(=O)N)CSC(=O)N
Properties
C5H11NS2
Molar mass 149.27 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Nereistoxin is a natural product identified in 1962 as the toxic organic compound N,N-dimethyl-1,2-dithiolan-4-amine. It had first been isolated in 1934 from the marine annelid Lumbriconereis heteropoda and acts by blocking the nicotinic acetylcholine receptor. [1] Researchers at Takeda in Japan investigated it as a possible insecticide. They subsequently developed a number of derivatives that were commercialised, [2] [3] including those with the ISO common names [4] bensultap, [5] cartap, [6] thiocyclam [7] and thiosultap. [8] [9]

Contents

Structures and synthesis

Bensultap (R=SO2Ph) was made by the reaction of the sodium salt of benzenethiolsulfonate (PhSO2SNa) with N,N-dimethyl 1,3-dichloro-2-propylamine or N,N-dimethyl 2,3-dichloropropylamine in ethanol. [9]

Bensultap synthesis.png

Bensultap can be converted to nereistoxin by treatment with alkali. [9]

History

Japanese fishermen used the annelid worm Lumbriconereis heteropoda as bait but after accidental human poisonings the chemical agent responsible was identified and named nereistoxin. [10] In the 1960s, researchers at Takeda Chemical Industries synthesised the active material N,N-dimethyl-1,2-dithiolan-4-amine and derivatives in which the sulfur-sulfur bond of the 1,2-dithiolane ring was replaced by alternative sulfur-linked groups. The resulting compounds were in many cases less toxic to mammals than the natural product while retaining good activity on insects. It was subsequently shown that all the compounds which were commercialised acted by being propesticides — breaking down in the environment to nereistoxin or a toxic dithiol. [11] [12]

Mechanism of action

Nereistoxin has chemical similarity to acetylcholine and its mode of action was suggested originally as being possibly by interference with acetylcholinesterase. Later electrophysiological studies using synapses from the cockroach Periplaneta americana showed that it acts by blocking the nicotinic acetylcholine receptor / ion channel complex in the insect central nervous system. This is also the mode of action of the related insecticides, all of which can produce the dithiol corresponding to cleavage of the 1,2-thiolane ring in the parent compound. [12] [13] [14]

Usage

None of the insecticidal analogues of nereistoxin became major products in agriculture and their use was mainly limited to Japanese and Chinese cultivation of rice, where their control of pests such as the rice stem borer Chilo suppressalis was significant. [9] They were not licensed for use in Europe or the USA. The limited success of this group of chemicals was partly due to other compounds having similar modes of action but higher potency and mammalian safety becoming available. [15]

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References

  1. ↑ Teuber, Lene (1990). "Naturally Occurring 1,2-Dithiolanes and 1,2,3-Trithianes. Chemical and Biological Properties". Sulfur Reports. 9 (4): 257–333. doi:10.1080/01961779008048732.
  2. ↑ Roberts, Terry R; Hutson, David H, eds. (2007). "Nereistoxin precursors". Metabolic Pathways of Agrochemicals. pp. 127–138. doi:10.1039/9781847551375-00127. ISBN   978-0-85404-499-3.
  3. ↑ Lewis, Kathleen A.; Tzilivakis, John; Warner, Douglas J.; Green, Andrew (2016). "An international database for pesticide risk assessments and management". Human and Ecological Risk Assessment. 22 (4): 1050–1064. doi:10.1080/10807039.2015.1133242. hdl: 2299/17565 . S2CID   87599872.
  4. ↑ "Compendium of Pesticide Common Names". BCPC.
  5. ↑ Pesticide Properties Database. "Bensultap". University of Hertfordshire.
  6. ↑ Pesticide Properties Database. "Cartap". University of Hertfordshire.
  7. ↑ Pesticide Properties Database. "Thiocyclam". University of Hertfordshire.
  8. ↑ Pesticide Properties Database. "Thiosultap". University of Hertfordshire.
  9. 1 2 3 4 Konishi, Kazuo (1968). "New Insecticidally Active Derivatives of Nereistoxin". Agricultural and Biological Chemistry. 32 (5): 678–679. doi: 10.1271/bbb1961.32.678 .
  10. ↑ Chiba, Sukehiro, et al. (1967). "Nereistoxin and its derivatives, their neuromuscular blocking and convulsive actions" (pdf). The Japanese Journal of Pharmacology. 17 (3): 491–492. doi: 10.1254/jjp.17.491 . PMID   4384262.
  11. ↑ Lee, Seog-Jong; Caboni, Pierluigi; Tomizawa, Motohiro; Casida, John E. (2004). "Cartap Hydrolysis Relative to Its Action at the Insect Nicotinic Channel". Journal of Agricultural and Food Chemistry. 52 (1): 95–98. doi:10.1021/jf0306340. PMID   14709019.
  12. 1 2 Casida, John E.; Durkin, Kathleen A. (2013). "Neuroactive Insecticides: Targets, Selectivity, Resistance, and Secondary Effects". Annual Review of Entomology. 58: 99–117. doi:10.1146/annurev-ento-120811-153645. PMID   23317040.
  13. ↑ Sattelle, DB, et al. (1985). "Nereistoxin: Actions on a CNS Acetylcholine Receptor / Ion Channel in the Cockroach Periplaneta Americana" (PDF). Journal of Experimental Biology. 118: 37–52. doi:10.1242/jeb.118.1.37.
  14. ↑ Copping, Leonard G; Hewitt, H. Geoffrey, eds. (1998). "Insecticides". Chemistry and Mode of Action of Crop Protection Agents. pp. 46–73. doi:10.1039/9781847550422-00046. ISBN   978-0-85404-559-4.
  15. ↑ Jeschke, Peter; Nauen, Ralf; Beck, Michael Edmund (2013). "Nicotinic Acetylcholine Receptor Agonists: A Milestone for Modern Crop Protection". Angewandte Chemie International Edition. 52 (36): 9464–9485. doi:10.1002/anie.201302550. PMID   23934864.

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