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| ImageFile = 1,2,3-Benzothiadiazole.png
| ImageFile = 1,2,3-Benzothiadiazole.png
| OtherNames = {{Unbulleted list|Benzothiadiazole|Benzthiadiazole|Azabenzothiadiazole|benzo-1,2,3-thiadiazole}}
| OtherNames = {{Unbulleted list|Benzothiadiazole|Benzthiadiazole|Azabenzothiadiazole|benzo-1,2,3-thiadiazole}}
| IUPACName = 1,2,3-Benzothiadiazole
| PIN = 1,2,3-Benzothiadiazole
| SystematicName = 1,2,3-Benzothiadiazole
| Section1 = {{Chembox Identifiers
| Section1 = {{Chembox Identifiers
| PubChem = 67505
| PubChem = 67505
| CASNo = 273-77-8
| CASNo = 273-77-8
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = R3PA3EL3RP
| EC_number = 205-989-4
| EC_number = 205-989-4
| MeSHName = benzo-1,2,3-thiadiazole
| MeSHName = benzo-1,2,3-thiadiazole
Line 20: Line 21:
| MeltingPtC = 36-37
| MeltingPtC = 36-37
| BoilingPtC = 220.5
| BoilingPtC = 220.5
| Density = 1.499 g/cm<sup>3</sup><ref name=Keith/>
| Appearance = colorless solid
}}
}}
| Section3 =
| Section3 =
Line 29: Line 32:
}}
}}


'''1,2,3-Benzothiadiazole''' is a [[bicyclic molecule|bicyclic]] [[Aromaticity|aromatic chemical]] composed of a [[benzene]] ring that is [[fused-ring compound|fused]] to a [[thiadiazoles|1,2,3-thiadiazole]].
'''1,2,3-Benzothiadiazole''' is a [[bicyclic molecule|bicyclic]] [[Aromaticity|aromatic chemical]] composed of a [[benzene]] ring that is [[fused-ring compound|fused]] to a [[thiadiazoles|1,2,3-thiadiazole]]. A colorless solid, the compound is soluble in organic solvents.

== Preparation ==
== Preparation ==
1,2,3-Benzothiadiazole is readily prepared by the [[diazotisation]] reaction of [[2-Aminothiophenol|2-aminothiophenol]] or its [[disulfide]] with [[sodium nitrite]], as originally reported in 1887<ref>{{cite journal |doi=10.1002/cber.188702001423 |title=Zur Kenntniss der orthoamidirten aromatischen Mercaptane |last1=Jacobson |first1=J. |journal=Berichte der deutschen chemischen Gesellschaft |year=1887 |volume=20 |pages=1895-1903 }}</ref> and reviewed in several subsequent publications.<ref name=Hodgson>{{cite journal |doi=10.1111/j.1478-4408.1948.tb02498.x |title=A Review of the Chemistry of the Arylthiadiazoles or Internal Diazo–Sulphides |last1=Hodgson |first1=H.H. |last2=Dodoson |first2=D.P. |journal=Journal of the Society of Dyers and Colourists |year=1964 |issue=2 |pages=65-71 }}</ref><ref>{{cite book |doi=10.1016/B978-008096519-2.00092-8 |chapter=1,2,3-Thiadiazoles and their Benzo Derivatives |title=Comprehensive Heterocyclic Chemistry |year=1984 |last1=Thomas |first1=E.W. |pages=447–462 |isbn=9780080965192 }}</ref><ref>{{cite book |title= Science of Synthesis |volume= 13: Category 2, Hetarenes and Related Ring Systems |editor1-last= Storr |editor1-first= R. C. |editor2-last= Gilchrist |editor2-first= T. L. |year= 2004 |chapter-title= |doi= 10.1055/sos-SD-013-00386 |chapter= Product Class 9: 1,2,3-Thiadiazoles}}</ref><ref>{{cite book |isbn=9783131812445 |title=Houben-Weyl Methods of Organic Chemistry Vol. E 8d, 4th Edition Supplement: Hetarenes III (Five-Membered Rings with Two and More Heteroatoms in the Ring System) - Part 4 |date=14 May 2014 |pages=93–104 |chapter=1,2,3-Benzothiadiazole }}</ref>
1,2,3-Benzothiadiazole is readily prepared by the [[diazotisation]] reaction of [[2-Aminothiophenol|2-aminothiophenol]] or its [[disulfide]] with [[sodium nitrite]], as originally reported in 1887<ref>{{cite journal |doi=10.1002/cber.188702001423 |title=Zur Kenntniss der orthoamidirten aromatischen Mercaptane |last1=Jacobson |first1=J. |journal=Berichte der Deutschen Chemischen Gesellschaft |year=1887 |volume=20 |pages=1895–1903 }}</ref> and reviewed in several subsequent publications.<ref name=Hodgson>{{cite journal |doi=10.1111/j.1478-4408.1948.tb02498.x |title=A Review of the Chemistry of the Arylthiadiazoles or Internal Diazo–Sulphides |last1=Hodgson |first1=H.H. |last2=Dodoson |first2=D.P. |journal=Journal of the Society of Dyers and Colourists |year=1964 |volume=64 |issue=2 |pages=65–71 }}</ref><ref>{{cite book |doi=10.1016/B978-008096519-2.00092-8 |chapter=1,2,3-Thiadiazoles and their Benzo Derivatives |title=Comprehensive Heterocyclic Chemistry |year=1984 |last1=Thomas |first1=E.W. |pages=447–462 |isbn=9780080965192 }}</ref><ref>{{cite book |title= Science of Synthesis |volume= 13: Category 2, Hetarenes and Related Ring Systems |editor1-last= Storr |editor1-first= R. C. |editor2-last= Gilchrist |editor2-first= T. L. |year= 2004 |doi= 10.1055/sos-SD-013-00386 |chapter= Product Class 9: 1,2,3-Thiadiazoles|isbn= 9783131122810 }}</ref><ref>{{cite book |isbn=9783131812445 |title=Houben-Weyl Methods of Organic Chemistry Vol. E 8d, 4th Edition Supplement: Hetarenes III (Five-Membered Rings with Two and More Heteroatoms in the Ring System) - Part 4 |date=14 May 2014 |pages=93–104 |chapter=1,2,3-Benzothiadiazole |publisher=Georg Thieme Verlag }}</ref>
:[[File:1,2,3-Benzothiadiazole synthesis.png|400px]]
:[[File:1,2,3-Benzothiadiazole synthesis.png|400px]]

The crystal structure was published in 2005.<ref>{{cite journal |doi=10.5517/cc9618s |year=2005 |last1=Palmer |first1=M. |last2=Parsons |first2=S. |last3=Messenger |first3=D. |title=CCDC 273924: Experimental Crystal Structure Determination |publisher=Cambridge Crystallographic Data Centre }}</ref>
By the [[Herz reaction]] [[aniline]]s can be converted to benzothiadiazole. The method is attractive since less elaborate precursors (merely anilines) are required. Upon treatment with [[disulfur dichloride]], the anilines give the intermediate 1,3,2-benzothiazathiolium salt, which is diazotised to complete the formation of a 1,2,3-benzothiadiazole. The parent system cannot be made this way, since the use of aniline in this reaction leads to formation of the 6-chloro derivative.<ref name=Kirby/>

==Structure and bonding==
The molecule is planar. The N-N and S-N distances are respectively 128 and 171 [[picometer]]s, indicative of multiple bond character.<ref name=Keith>{{cite journal |doi=10.1016/0022-328X(91)86290-7 |title=Transition metal heterocyclic chemistry: XI. Manganese cyclopentadienyldicarbonyl complexes of 1,2,3-selena- and thiadiazoles including structural comparison of free and complexed 1,2,3-benzothiadiazole and 4-phenyl-1,2,3-thiadiazole |year=1991 |last1=Mayr |first1=Armin J. |last2=Carrasco-Flores |first2=Benjamin |last3=Cervantes-Lee |first3=Francisco |last4=Pannell |first4=Keith H. |last5=Párkányi |first5=László |last6=Raghuveer |first6=Krishan |journal=Journal of Organometallic Chemistry |volume=405 |issue=3 |pages=309–322 }}
</ref> Like [[naphthalene]], this heterocycle is a 10-electron system.<ref name=Hodgson />


== Reactions ==
== Reactions ==
The extent of the aromaticity of the compound was examined by comparison with [[napthalene]], which allowed the conclusion that it behaved as a 10-electron system in which the sulfur atom contributed its lone pair to the [[Resonance (chemistry)|resonance]] structures, in accordance with [[Hückel's rule]].<ref name=Hodgson /> However, 1,2,3-benzothiadiazole is much less reactive than napthalene in its [[electrophilic aromatic substitution]] chemistry, for example only forming nitro derivatives under forcing conditions.<ref>{{cite journal |doi=10.1039/JR9630004794 |title=1,2,3-Benzothiadiazole. Part II. Electrophilic substitution in 4- and 6-amino-1,2,3-benzothiadiazoles |year=1963 |last1=Ward |first1=E. R. |last2=Heard |first2=D. D. |journal=Journal of the Chemical Society (Resumed) |pages=4794-4803 }}</ref> For that reason, many of its simple derivatives have been made either from already-substituted 2-aminothiophenols or by the [[Herz reaction]] in which a substituted [[aniline]] is treated with [[disulfur dichloride]] and the intermediate 1,3,2-benzothiazathiolium salt is diazotised to complete the formation of a 1,2,3-benzothiadiazole. The parent system cannot be made this way, since the use of aniline in this reaction leads to formation of the 6-chloro derivative.<ref>{{cite journal |doi=10.1039/J39700002250 |title=1,2,3-Benzothiadiazoles. Part I. A simplified synthesis of 1,2,3-benzothiadiazoles |year=1970 |last1=Kirby |first1=P. |last2=Soloway |first2=S. B. |last3=Davies |first3=J. H. |last4=Webb |first4=Shirley B. |journal=Journal of the Chemical Society C: Organic |issue=16 |page=2250 }}</ref>
1,2,3-benzothiadiazole is much less nucleophilic than naphthalene. [[Nitration]] is slow.<ref>{{cite journal |doi=10.1039/JR9630004794 |title=1,2,3-Benzothiadiazole. Part II. Electrophilic substitution in 4- and 6-amino-1,2,3-benzothiadiazoles |year=1963 |last1=Ward |first1=E. R. |last2=Heard |first2=D. D. |journal=Journal of the Chemical Society (Resumed) |pages=4794–4803 }}</ref> For that reason, many of its simple derivatives have been made from 2-aminothiophenols already having additional substituents.<ref name=Kirby>{{cite journal |doi=10.1039/J39700002250 |title=1,2,3-Benzothiadiazoles. Part I. A simplified synthesis of 1,2,3-benzothiadiazoles |year=1970 |last1=Kirby |first1=P. |last2=Soloway |first2=S. B. |last3=Davies |first3=J. H. |last4=Webb |first4=Shirley B. |journal=Journal of the Chemical Society C: Organic |issue=16 |page=2250 }}</ref>


1,2,3-benzothiadiazole is a very weak base and [[alkylation]] reactions give exclusively the 3-amino [[Quaternary ammonium cation|quaternary salt]].<ref>{{cite journal |doi=10.1039/J39700002060 |title=1,2,3-Benzothiadiazole. Part VI. Investigations on the quaternisation of 1,2,3-benzothiadiazole and 1,2,3-benzoselenadiazole |year=1970 |last1=Jaffari |first1=G. A. |last2=Nunn |first2=A. J. |last3=Ralph |first3=J. T. |journal=Journal of the Chemical Society C: Organic |issue=15 |page=2060 }}</ref>
1,2,3-benzothiadiazole is a very weak base and [[alkylation]] reactions give exclusively the 3-amino [[Quaternary ammonium cation|quaternary salt]].<ref>{{cite journal |doi=10.1039/J39700002060 |title=1,2,3-Benzothiadiazole. Part VI. Investigations on the quaternisation of 1,2,3-benzothiadiazole and 1,2,3-benzoselenadiazole |year=1970 |last1=Jaffari |first1=G. A. |last2=Nunn |first2=A. J. |last3=Ralph |first3=J. T. |journal=Journal of the Chemical Society C: Organic |issue=15 |page=2060 }}</ref>


== Applications ==
== Applications ==
1,2,3-benzothiadiazole has been claimed to [[Synergy#Biological_sciences|synergise]] [[insecticides]] including [[dicrotophos]]<ref>{{cite journal |doi=10.1021/jf60170a011 |title=Benzothiadiazoles, a novel group of insecticide synergists |year=1970 |last1=Felton |first1=John C. |last2=Jenner |first2=Donald W. |last3=Kirby |first3=Peter. |journal=Journal of Agricultural and Food Chemistry |volume=18 |issue=4 |pages=671–673 }}</ref> but has not been commercialised for that application. The only derivative to have found significant use is the [[fungicide]] [[acibenzolar-S-methyl]].
1,2,3-benzothiadiazole has been claimed to [[Synergy#Biological_sciences|synergise]] [[insecticides]] including [[dicrotophos]]<ref>{{cite journal |doi=10.1021/jf60170a011 |title=Benzothiadiazoles, a novel group of insecticide synergists |year=1970 |last1=Felton |first1=John C. |last2=Jenner |first2=Donald W. |last3=Kirby |first3=Peter. |journal=Journal of Agricultural and Food Chemistry |volume=18 |issue=4 |pages=671–673 }}</ref> but has not been commercialised for that application. The only derivative to have found significant use is the [[fungicide]] [[acibenzolar-S-methyl|acibenzolar-''S''-methyl]].


== References ==
== References ==

Latest revision as of 09:39, 11 January 2024

1,2,3-Benzothiadiazole
Names
Preferred IUPAC name
1,2,3-Benzothiadiazole
Other names
  • Benzothiadiazole
  • Benzthiadiazole
  • Azabenzothiadiazole
  • benzo-1,2,3-thiadiazole
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 205-989-4
MeSH benzo-1,2,3-thiadiazole
UNII
  • InChI=1S/C6H4N2S/c1-2-4-6-5(3-1)7-8-9-6/h1-4H
    Key: FNQJDLTXOVEEFB-UHFFFAOYSA-N
  • C1=CC=C2C(=C1)N=NS2
Properties
C6H4N2S
Molar mass 136.17 g·mol−1
Appearance colorless solid
Density 1.499 g/cm3[1]
Melting point 36–37 °C (97–99 °F; 309–310 K)
Boiling point 220.5 °C (428.9 °F; 493.6 K)
Related compounds
Related compounds
 2,1,3-Benzothiadiazole
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

1,2,3-Benzothiadiazole is a bicyclic aromatic chemical composed of a benzene ring that is fused to a 1,2,3-thiadiazole. A colorless solid, the compound is soluble in organic solvents.

Preparation

[edit]

1,2,3-Benzothiadiazole is readily prepared by the diazotisation reaction of 2-aminothiophenol or its disulfide with sodium nitrite, as originally reported in 1887[2] and reviewed in several subsequent publications.[3][4][5][6]

By the Herz reaction anilines can be converted to benzothiadiazole. The method is attractive since less elaborate precursors (merely anilines) are required. Upon treatment with disulfur dichloride, the anilines give the intermediate 1,3,2-benzothiazathiolium salt, which is diazotised to complete the formation of a 1,2,3-benzothiadiazole. The parent system cannot be made this way, since the use of aniline in this reaction leads to formation of the 6-chloro derivative.[7]

Structure and bonding

[edit]

The molecule is planar. The N-N and S-N distances are respectively 128 and 171 picometers, indicative of multiple bond character.[1] Like naphthalene, this heterocycle is a 10-electron system.[3]

Reactions

[edit]

1,2,3-benzothiadiazole is much less nucleophilic than naphthalene. Nitration is slow.[8] For that reason, many of its simple derivatives have been made from 2-aminothiophenols already having additional substituents.[7]

1,2,3-benzothiadiazole is a very weak base and alkylation reactions give exclusively the 3-amino quaternary salt.[9]

Applications

[edit]

1,2,3-benzothiadiazole has been claimed to synergise insecticides including dicrotophos[10] but has not been commercialised for that application. The only derivative to have found significant use is the fungicide acibenzolar-S-methyl.

References

[edit]
  1. ^ a b Mayr, Armin J.; Carrasco-Flores, Benjamin; Cervantes-Lee, Francisco; Pannell, Keith H.; Párkányi, László; Raghuveer, Krishan (1991). "Transition metal heterocyclic chemistry: XI. Manganese cyclopentadienyldicarbonyl complexes of 1,2,3-selena- and thiadiazoles including structural comparison of free and complexed 1,2,3-benzothiadiazole and 4-phenyl-1,2,3-thiadiazole". Journal of Organometallic Chemistry. 405 (3): 309–322. doi:10.1016/0022-328X(91)86290-7.
  2. ^ Jacobson, J. (1887). "Zur Kenntniss der orthoamidirten aromatischen Mercaptane". Berichte der Deutschen Chemischen Gesellschaft. 20: 1895–1903. doi:10.1002/cber.188702001423.
  3. ^ a b Hodgson, H.H.; Dodoson, D.P. (1964). "A Review of the Chemistry of the Arylthiadiazoles or Internal Diazo–Sulphides". Journal of the Society of Dyers and Colourists. 64 (2): 65–71. doi:10.1111/j.1478-4408.1948.tb02498.x.
  4. ^ Thomas, E.W. (1984). "1,2,3-Thiadiazoles and their Benzo Derivatives". Comprehensive Heterocyclic Chemistry. pp. 447–462. doi:10.1016/B978-008096519-2.00092-8. ISBN 9780080965192.
  5. ^ Storr, R. C.; Gilchrist, T. L., eds. (2004). "Product Class 9: 1,2,3-Thiadiazoles". Science of Synthesis. Vol. 13: Category 2, Hetarenes and Related Ring Systems. doi:10.1055/sos-SD-013-00386. ISBN 9783131122810.
  6. ^ "1,2,3-Benzothiadiazole". Houben-Weyl Methods of Organic Chemistry Vol. E 8d, 4th Edition Supplement: Hetarenes III (Five-Membered Rings with Two and More Heteroatoms in the Ring System) - Part 4. Georg Thieme Verlag. 14 May 2014. pp. 93–104. ISBN 9783131812445.
  7. ^ a b Kirby, P.; Soloway, S. B.; Davies, J. H.; Webb, Shirley B. (1970). "1,2,3-Benzothiadiazoles. Part I. A simplified synthesis of 1,2,3-benzothiadiazoles". Journal of the Chemical Society C: Organic (16): 2250. doi:10.1039/J39700002250.
  8. ^ Ward, E. R.; Heard, D. D. (1963). "1,2,3-Benzothiadiazole. Part II. Electrophilic substitution in 4- and 6-amino-1,2,3-benzothiadiazoles". Journal of the Chemical Society (Resumed): 4794–4803. doi:10.1039/JR9630004794.
  9. ^ Jaffari, G. A.; Nunn, A. J.; Ralph, J. T. (1970). "1,2,3-Benzothiadiazole. Part VI. Investigations on the quaternisation of 1,2,3-benzothiadiazole and 1,2,3-benzoselenadiazole". Journal of the Chemical Society C: Organic (15): 2060. doi:10.1039/J39700002060.
  10. ^ Felton, John C.; Jenner, Donald W.; Kirby, Peter. (1970). "Benzothiadiazoles, a novel group of insecticide synergists". Journal of Agricultural and Food Chemistry. 18 (4): 671–673. doi:10.1021/jf60170a011.
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