Diazonium compound

Benzenediazonium cation

Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group R−N+
2X−
 where R can be any organic group, such as an alkyl or an aryl, and X is an inorganic or organic anion, such as a halogen. Diazonium salts, especially those where R is an aryl group, are important intermediates in the organic synthesis of azo dyes.[1]

Preparation

The process of forming diazonium compounds is called "diazotation", "diazoniation", or "diazotization". The reaction was first reported by Peter Griess in 1858, who subsequently discovered several reactions of this new class of compounds. The most important method for the preparation of diazonium salts is treatment of aromatic amines such as aniline with nitrous acid. Usually the nitrous acid is generated in situ (in the same flask) from sodium nitrite and mineral acid. In aqueous solution diazonium salts are unstable at temperatures above 5 °C; the −N+≡N group tends to be lost as N2 (nitrogen gas). One can isolate diazonium compounds as tetrafluoroborate salts, which are stable at room temperature. Often, diazonium compounds are not isolated and once prepared, used immediately in further reactions. This approach is illustrated in the preparation of an arylsulfonyl compound:[2]

It is often preferred that the diazonium salt remain in solutions, but they do tend to supersaturate. Operators have been killed and injured by an unexpected crystallization of the salt followed by its detonation.[3]

Diazo coupling reactions

The most widely practiced reaction of diazonium salts is azo coupling. In this process, the diazonium compound is attacked by, i.e., coupled to, electron-rich substrates. When the coupling partners are arenes such as anilines and phenols, the process is an example of electrophilic aromatic substitution:

ArN+
2 + Ar′H → ArN2Ar′ + H+

Another commercially important class of coupling partners are acetoacetic amides, as illustrated by the preparation of Pigment Yellow 12, a diarylide pigment.[4]

The resulting azo compounds are often useful dyes and in fact are called azo dyes.[5] The deep colors of the dyes reflects their extended conjugation. For example, the dye called aniline yellow is produced by mixing aniline and cold solution of diazonium salt and then shaking it vigorously. Aniline yellow is obtained as an yellow solid.[6] Similarly, a cold basic solution of Naphthalen-2-ol (Β-naphthol) give the intensely orange-red precipitate.[6] Methyl orange is an example of an azo dye that is used in the laboratory as a pH indicator.

Displacement of the N2 group

Arenediazonium cations undergo several reactions in which the N2 group is replaced by another group or ion. Some of the major ones are the following.[7][8]


Replacement by Halogens

Sandmeyer reaction

Benzenediazonium chloride heated with cuprous chloride or cuprous bromide respectively dissolved in HCl or HBr yield chlorobenzene or bromobenzene, respectively.

C
6H
5N+
2 + CuCl → C6H5Cl + N2 + Cu+

Gatterman reaction

In the Gatterman reaction, benzenediazonium chloride is warmed with copper powder and HCl or HBr to produce chlorobenzene and bromobenzene respectively. It is named after the German chemist Ludwig Gattermann.[9]

C
6H
5N+
2 + CuX → C6H5X + N2 + Cu+

Replacement by iodide

Iodine is not easily introduced into the benzene ring directly. However it can be introduced by treating aryldiazonium cations with potassium iodide:

C
6H
5N+
2 + KI → C6H5I + K+ + N2

Replacement by fluoride

Fluorobenzene is produced by thermal decomposition of benzenediazonium fluoroborate. The reaction is called the Balz-Schiemann reaction.[10]

[C
6H
5N+
2]BF−
4 → C6H5F + BF3 + N2

Miscellaneous Replacements

Replacement by hydrogen

Arenediazonium cations are reduced by hypophosphorous acid or sodium stannite gives benzene:

[C
6H
5N+
2]Cl− + H3PO2 + H2O → C6H6 + N2 + H3PO3 + HCl

Replacement by a hydroxyl group

Phenols are produced by heating aqueous solutions of aryldiazonium salts to 100 °C.

C
6H
5N+
2 + H2O → C6H5OH + N2 + H+

This reaction goes by the German name Phenolverkochung ("cooking down to yield phenols"). The phenol formed may react with the diazonium salt and hence the reaction is carried in the presence of an acid which helps in suppressing this further reaction.

Replacement by a nitro group

Nitrobenzene can be obtained by treating benzenediazonium fluoroborate with sodium nitrite in presence of copper. Alternatively, the diazotisation of the aniline can be conducted in presence of cuprous oxide, which generates cuprous nitrite in situ:

C
6H
5N+
2 + CuNO2 → C6H5NO2 + N2 + Cu+

Replacement by a cyano group

The cyano group usually cannot be introduced by nucleophilic substitution of haloarenes, but such compounds can be easily prepared from diazonium salts. Illustrative is the preparation of benzonitrile using the reagent cuprous cyanide:

C
6H
5N+
2 + CuCN → C6H5CN + Cu+ + N2

This reaction is a special type of Sandmeyer reaction.

Replacement by a thiol group

Diazonium salts can be converted to thiols in a two-step procedure. Treatment of benzenediazonium chloride with potassium ethylxanthate followed by hydrolysis of the intermediate xanthate ester gives thiophenol:

C
6H
5N+
2 + C
2H
5OCS−
2 → C6H5SC(S)OC2H5
C6H5SC(S)OC2H5 + H2O → C6H5SH + HOC(S)OC2H5

Replacement by an aryl group

The aryl group can be coupled to another using aryldiazonium salts. For example, treatment of benzenediazonium chloride with benzene (an aromatic compound) in the presence of sodium hydroxide gives diphenyl:

[C
6H
5N+
2]Cl− + C6H6 → C6H5−C6H5 + N2 + HCl

This reaction is known as the Gomberg–Bachmann reaction. A similar conversion is also achieved by treating benzenediazonium chloride with ethanol and copper powder.

Replacement by a carboxyl group

Diazonium fluoroborates react with an aliphatic carboxylic acid yield the corresponding benzoic acid. This reaction provides a method to prepare aromatic carboxylic acids from aliphatic carboxylic acids:

[C
6H
5N+
2]BF−
4 + RCO2H → C6H5CO2H + BF3 + N2 + RF

Meerwein reaction

Benzenediazonium chloride reacts with compounds containing activated double bonds to produces phenylated products. The reaction is called the Meerwein arylation:

[C
6H
5N+
2]Cl− + ArCH=CHCO2H → ArC=C−C6H5 + N2 + CO2 + HCl

Metal complexes

In their reactions with metal complexes, diazonium cations behave similarly to NO+. For example, low-valent metal complexes add with diazonium salts. Illustrative complexes are [Fe(CO)2(PPh3)2(N2Ph)]+ and the chiral-at-metal complex Fe(CO)(NO)(PPh3)(N2Ph).[11]

Other methods for dediazotization

Grafting reactions

In a potential application in nanotechnology, the diazonium salts 4-chlorobenzenediazonium tetrafluoroborate very efficiently functionalizes single wall nanotubes.[13] In order to exfoliate the nanotubes, they are mixed with an ionic liquid in a mortar and pestle. The diazonium salt is added together with potassium carbonate, and after grinding the mixture at room temperature the surface of the nanotubes are covered with chlorophenyl groups with an efficiency of 1 in 44 carbon atoms. These added subsituents prevent the tubes from forming intimate bundles due to large cohesive forces between them, which is a recurring problem in nanotube technology.

It is also possible to functionalize silicon wafers with diazonium salts forming an aryl monolayer. In one study, the silicon surface is washed with ammonium hydrogen fluoride leaving it covered with silicon–hydrogen bonds (hydride passivation).[14] The reaction of the surface with a solution of diazonium salt in acetonitrile for 2 hours in the dark is a spontaneous process through a free radical mechanism:[15]

So far grafting of diazonium salts on metals has been accomplished on iron, cobalt, nickel, platinum, palladium, zinc, copper and gold surfaces. Also grafting to diamond surfaces has been reported.[16] One interesting question raised is the actual positioning on the aryl group on the surface. An in silico study [17] demonstrates that in the period 4 elements from titanium to copper the binding energy decreases from left to right because the number of d-electrons increases. The metals to the left of iron are positioned tilted towards or flat on the surface favoring metal to carbon pi bond formation and those on the right of iron are positioned in an upright position, favoring metal to carbon sigma bond formation. This also explains why diazonium salt grafting thus far has been possible with those metals to right of iron in the periodic table.

Reduction to a hydrazine group

Diazonium salts can be reduced with stannous chloride (SnCl2) to the corresponding hydrazine derivatives. This reaction is particularly useful in the Fischer indole synthesis of triptan compounds and indometacin. The use of sodium dithionite is an improvement over stannous chloride since it is a cheaper reducing agent with fewer environmental problems.

Applications

The first use of diazonium salts was to produce water-fast dyed fabrics by immersing the fabric in an aqueous solution of the diazonium compound, followed by immersion in a solution of the coupler (the electron-rich ring that undergoes electrophilic substitution). The major applications of diazonium compounds remains in the dye and pigment industry.[5]

Other uses

Diazonium compounds are standard reagents used in synthesis of organic compounds, especially aryl derivatives.

Diazonium salts are light sensitive and break down under near UV or violet light. This property has led to their use in document reproduction. In this process, paper or film is coated with a diazonium salt. After contact exposure under light, the residual diazo is converted to a stable azo dye with an aqueous solution of coupler. A more common process uses a paper coated with diazo, coupler and an acid to inhibit coupling; after exposure the image is developed by a vapor mixture of ammonia and water which forces coupling.

Safety

Solid diazonium halides are often dangerously explosive, and fatalities and injuries have been reported.[3]

The nature of the anions affects stability of the salt. Aryl diazonium perchlorates, such as nitrobenzenediazonium perchlorate, have been used to initiate explosives.

See also

References

  1. ↑ Chemistry of the Diazonium and Diazo Groups: Part 1. S. Patai, Ed. 1978 Wiley-Blackwell. ISBN 0-471-99492-8. Chemistry of the Diazonium and Diazo Groups: Part 2. S. Patai, Ed. 1978 Wiley-Blackwell. ISBN 0-471-99493-6.
  2. ↑ R. V. Hoffman (1990). "m-Trifluoromethylbenzenesulfonyl Chloride". Org. Synth.; Coll. Vol., 7, p. 508
  3. 1 2 "UK CRHF Incident Report - Supersaturated Diazonium salt causes Fatality". Retrieved 13 May 2010.
  4. ↑ K. Hunger. W. Herbst "Pigments, Organic" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012. doi:10.1002/14356007.a20_371
  5. 1 2 Klaus Hunger, Peter Mischke, Wolfgang Rieper, Roderich Raue, Klaus Kunde, Aloys Engel "Azo Dyes" in Ullmann’s Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a03_245.
  6. 1 2 Clark, Jim. "chemguide". Retrieved 28 September 2011.
  7. ↑ March, J. “Advanced Organic Chemistry” 4th Ed. J. Wiley and Sons, 1992: New York. ISBN 978-0-471-60180-7.
  8. ↑ Marye Anne Fox; James K. Whitesell (2004). Organic Chemistry (3, illustrated ed.). Jones & Bartlett Learning. pp. 535–538. ISBN 978-0-7637-2197-8.
  9. ↑ L. Gattermann (1894). "Untersuchungen über Diazoverbindungen". Berichte der deutschen chemischen Gesellschaft. 23 (1): 1218–1228. doi:10.1002/cber.189002301199.
  10. ↑ Flood, D. T. (1943). "Fluorobenzene". Org. Synth.; Coll. Vol., 2, p. 295.
  11. ↑ Sutton, D (1993). "Organometallic Diazo Compounds". Chem. Rev. 93: 905–1022. doi:10.1021/cr00019a008.
  12. ↑ DOI: 10.1002/anie.201309761, Ascorbic Acid as an Initiator for the Direct C-H Arylation of (Hetero)arenes with Anilines Nitrosated In Situ, Fernando Pinacho Crisóstomo, Tomás Martín, Romen Carrillo, Angew. Chem. Int. Ed. 2014, 53, 2181–2185.
  13. ↑ Green Chemical Functionalization of Single-Walled Carbon Nanotubes in Ionic Liquids B. Katherine Price, Jared L. Hudson, and James M. Tour J. Am. Chem. Soc.; 2005; 127(42) pp. 14867–14870. doi:10.1021/ja053998c
  14. ↑ Michael P. Stewart; Francisco Maya; Dmitry V. Kosynkin; Shawn M. Dirk; Joshua J. Stapleton; Christine L. McGuiness; David L. Allara; James M. Tour (2004). "Direct Covalent Grafting of Conjugated Molecules onto Si, GaAs, and Pd Surfaces from Aryldiazonium Salts". J. Am. Chem. Soc. 126 (1): 370–8. PMID 14709104. doi:10.1021/ja0383120.
  15. ↑ Reaction sequence: silicon surface reaction with ammonium hydrogen fluoride creates hydride layer. An electron is transferred from the silicon surface to the diazonium salt in an open circuit potential reduction leaving a silicon radical cation and a diazonium radical. In the next step a proton and a nitrogen molecule are expelled and the two radical residues recombine creating a surface silicon to carbon bond.
  16. ↑ S.Q. Lud; M. Steenackers; P. Bruno; D.M. Gruen; P. Feulner; J.A. Garrido; M. Stutzmann (2006). "Chemical Grafting of Biphenyl Self-Assembled Monolayers on Ultrananocrystalline Diamond". J. Am. Chem. Soc. 128 (51): 16884–91. PMID 17177439. doi:10.1021/ja0657049.
  17. ↑ De-en Jiang; Bobby G. Sumpter; Sheng Dai (2006). "Structure and Bonding between an Aryl Group and Metal Surfaces". J. Am. Chem. Soc. 128 (18): 6030–1. PMID 16669660. doi:10.1021/ja061439f.
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