Author Topic: Diazonium salts in Iodobenzene synthesis  (Read 1691 times)

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Diazonium salts in Iodobenzene synthesis
« on: June 11, 2003, 12:10:00 AM »
Diazonium salts can be reacted with KI to produce aryl iodides,

C6H5N(+)=–N ------------KI-------------> C6H5I        +    N2
 (diazonium salt) (Potssium iodide)          (aryliodide)
 
where the diazonium salts are generated with ,

C6H5NH3 + HONO----> ArN(+)=-N   (Ref.March's 5th edition page 819 "diazotization")
(aniline)      (nitrous acid)      (diazonium salt)

"replacement of the diazonium group by I does not require the use of cuprous halide or copper, the diazonium salt and potassium iodide are simply mixed together and allowed to react."(Ref.Morrison and Boyd  2nd, editon page 776)
this is not a Sandmeyer reaction.

Looking through several chemical sources both aniline and Potassium iodide are relatively inexpensive as  obtainable starting material to synthecise aryliodides which can be useful for the enolate method for bee's.....java

Ref.
Wu,Z.;Moore,J.S. Tetrahedron Lett. 35,5539,1994
March's 5th edition pg. 875"Iodo-de-diazoniation"

Organic Syntheses, CV 2, 351

(http://www.orgsyn.org/orgsyn/prep.asp?prep=CV2P0351)

Post 219073 (missing)

(foxy2: "Iodobenzene from Aniline", Chemistry Discourse)



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Re: Novel easy preparations of Iodobenzene.....
« Reply #1 on: September 15, 2003, 02:09:00 AM »
(The link is above is  now fixed for direct downloading the  pdf of the excellent article on the synthesis of Iodobenzene........)


Novel Easy Preparations of Some Aromatic Iodine(I, III, and V) Reagents, Widely Applied in Modern Organic Synthesis *

Lech Skulski

Molecules 8, 45-52,2003

http://www.mdpi.org/molecules/papers/80100045.pdf




Abstract:... We report our novel (or considerably improved) methods for the synthesis of aromatic iodides, (dichloroiodo)arenes, (diacetoxyiodo)arenes, [bis(trifluoroacetoxy)-iodo]arenes, iodylarenes and diaryliodonium salts, as well as some facile, oxidative anion
metatheses in crude diaryliodonium or tetraalkylammonium halides and, for comparison,potassium halides. All our formerly published papers were discussed and explained in our review ÒOrganic Iodine(I, III, and V) Chemistry: 10 Years of Development at the Medical University of Warsaw, PolandÓ (1990-2000) [1].


Conclusions,..This lecture shows our small groupÕs main interest in developing novel (or considerably improved) preparative procedures, which are suitable for easy, quick, cheap, and possibly enviromentally benign preparations of iodoarenes and some basic aromatic hypervalent iodine reagents: ArICl2, ArI(OAc)2, ArI(OCOCF3)2, ArIO2, and diaryliodonium salts with substantially non-nucleophilic counter ions (suitable for the arylation of organic and inorganic nucleophiles). Our earlier works (1990-2000) are Molecules 2003, 8,51 related and discussed in our extensive review [1]; in this lecture our works published in 2001 [4, 7, 8,10, 13] are also covered and referred to, as well as those published in 2002 [6, 11, 12].

References

[1] Skulski, L. Organic Iodine(I, III, and V) Chemistry: 10 Years of Development at the Medical
University of Warsaw, Poland. Molecules 2000, 5 (12), 1331-1371; Avail. at URL:

http://www.mdpi.org/molecules/papers/51201331.pdf


[2] (a) Roedig, A. In Houben-Weyl, Methoden der organischen Chemie; Thieme Verlag: Stuttgart,
4th ed., 1960, vol. 5/4a, p 574; (b) Merkushev, E. B. Advances in the Synthesis of Iodoaromatic
Compounds. Synthesis 1988, 923-937; (c) Sasson, Y. In The Chemistry of Halides, Pseudo-
Halides and Azides, Supplement D1; ed. by Patai, S. and Rappoport, Z.; Wiley-Interscience:
Chichester, 1995, p 535.
[3] (a)Varvoglis, A. The Organic Chemistry of Polycoordinated Iodine; VCH: Weinheim, 1992; (b)
Stang, P. J.; Zhdankin, V. V. Organic Polyvalent Iodine Compounds. Chem. Rev. 1996, 96, 1123-
1178; (c) Varvoglis, A. Hypervalent Iodine in Organic Synthesis; Academic Press: San Diego,
1997; (d) Zhdankin, V. V.; Stang, P. J. Recent Developments in the Chemistry of Polyvalent
Iodine Compounds. Chem. Rev. 2002, 102, 2523-2584.
[4] Skulski, L.; Wroczynski, P. Some Heteroaromatic Organomercurials, Their Syntheses and
Reactions: A Review of Our Research (1980 Ð 2000). Molecules 2001, 6 (12), 927-958; Avail. at
URL:

http://www.mdpi.org/molecules/papers/61200927.pdf

.
[5] Skulski, L. with co-workers, the experiments just completed for their publishing.
[6] Sosnowski, M.; Skulski, L. Microwawe-Accelerated Iodination of Some Aromatic Amines,
Using Urea-Hydrogen Peroxide Addition Compound (UHP) as the Oxidant. Molecules 2002, 7
(12), 867-880; Avail. at URL:

http://www.mdpi.org./molecules/papers/71200867.pdf

.
[7] Lulinski, P.; Obeid, N.; Skulski, L. One-Pot Preparations of (Dichloroiodo)arenes from Some
Arenes. Bull. Chem. Soc. Jpn. 2001, 74, 2433-2434.
[8] Obeid, N.; Skulski, L. One-Pot Procedures for Preparing (Dichloroiodo)arenes from Arenes and
Diiodine, with Chromium(VI) Oxide as the Oxidant. Molecules 2001, 6 (11), 869-874; Avail. at
URL:

http://www.mdpi.org/molecules/papers/61100869.pdf

.
[9] McKillop, A.; Kemp, D. Further Functional Group Oxidations Using Sodium Perborate.
Tetrahedron 1989, 45, 3299-3306.
[10] Kazmierczak, P.; Skulski, L.; Kraszkiewicz, L. Syntheses of (Diacetoxyiodo)arenes or
Iodylarenes from Iodoarenes, with Sodium Periodate as the Oxidant. Molecules 2001, 6 (11),
881-891; Avail. at URL:

http://www.mdpi.org/molecules/papers/61100881.pdf

.
[11] Kazmierczak, P.; Skulski, L. Easy Preparation of [Bis(trifluoroacetoxy)iodo]arenes from
Iodoarenes, with Sodium Percarbonate as the Oxidant. Molecules 2002, 7 (11), 810-812; Avail. at
URL:

http://www.mdpi.org/molecules/papers/71100810.pdf

.
[12] Zielinska, A.; Skulski, L. Easy Preparation of (Diacetoxyiodo)arenes from Iodoarenes, with
Sodium Percarbonate as the Oxidant. Molecules 2002, 7 (11), 806-809; Avail. at URL.


Note.... This is a must Aryl-halogen in the enolate synthesis of P2P where enolated  acetone is added  to the iodobenzene either with K, or Na, in an ammonia base solvent ......java