ChemInform Abstract: REACTION OF TRIFLUOROMETHANESULFONIC ACID ANHYDRIDE WITH ARYLDIAZONIUM TETRAFLUOROBORATES

Nazaretyan, V. P.; Kamenskaya, O. I.

doi:10.1002/chin.197628203

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“…After a workup identical to that described above for the preparation of 3a, the pure title compound was obtained in 76% yield (0.98 g); bp 114¡C/20 Torr (Lit. 8 bp 108¡C/25 Torr). Anal.…”

Section: P-chlorophenyl Trifluoromethanesulfonate (6c); Typical Procementioning

confidence: 99%

“…5 It is known that aryl trifluoromethanesulfonates can be prepared by triflation of phenols or of their O -silyl derivatives, 6 as well as by thermal decomposition of arenediazonium tetrafluoroborates in trifluoromethanesulfonic acid 7 or, though less favourably, in trifluoromethanesulfonic anhydride. 8 Instead, to our knowledge, aryl methanesulfonates are prepared exclusively by treating phenols with methanesulfonyl chloride in the presence of a base. 9Ð13 Recently 14 we prepared a representative series of dry arenediazonium salts 1 that are very stable due to the anion of the o -benzenedisulfonimide ( 4 ), promptly prepared and able to be stored safely for long periods, without any risk and ready for use.…”

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A Simple Preparation of Aryl Methanesulfonates by Thermal Decomposition of Dry Arenediazonium o-Benzenedisulfonimides in Methanesulfonic Acid

Barbero¹,

Degani²,

Dughera³

et al. 1999

Synthesis

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Aryl methanesulfonates 3 (18 examples) were easily prepared by thermal decomposition of dry arenediazonium o -benzenedisulfonimides 1 in methanesulfonic acid ( 2 ). The reactions were carried out at temperatures between 60 and 120¡C for times between 0.5 and 8 h. The aryl methanesulfonates were obtained in reproducible yield of 70Ð90%, with few exceptions. In all cases the o -benzenedisulfonimide ( 4 ) could be recovered in good yields which can then be reused to prepare the salts 1 . When thermal decomposition of salts 1 was carried out in trifluoromethanesulfonic acid ( 5 ) at 90Ð120¡C for 1Ð2 h, aryl trifluoromethanesulfonates 6 were obtained in 73Ð78% yield (3 examples).Aryl methanesulfonates 3 are a notable class of compounds with various applications. They are used in organic synthesis, in reactions where it is necessary to protect the phenolic hydroxyl group 1 or where there is the removal of the mesylate group, i.e. in metal-catalyzed homoand cross-coupling reactions 2 and in substitution reactions. 2b,3 Furthermore, the use of aryl methanesulfonates has been the subject of numerous patent claims, even recent ones, such as dyes, 1b,c drugs 4 and especially agrochemicals. 5 It is known that aryl trifluoromethanesulfonates can be prepared by triflation of phenols or of their O -silyl derivatives, 6 as well as by thermal decomposition of arenediazonium tetrafluoroborates in trifluoromethanesulfonic acid 7 or, though less favourably, in trifluoromethanesulfonic anhydride. 8 Instead, to our knowledge, aryl methanesulfonates are prepared exclusively by treating phenols with methanesulfonyl chloride in the presence of a base. 9Ð13 Recently 14 we prepared a representative series of dry arenediazonium salts 1 that are very stable due to the anion of the o -benzenedisulfonimide ( 4 ), promptly prepared and able to be stored safely for long periods, without any risk and ready for use. In a wide-ranging investigation 14,15 on the synthetic uses of the salts 1 , we have found that thermal decomposition in methanesulfonic acid ( 2 ) brings about their easy conversion into the corresponding aryl methanesulfonates 3 (Scheme 1). The reaction involved heating of the salts 1 in methanesulfonic acid ( 2 ) between 60 to 120¡C, temperatures that are at least 20ûC lower than the decomposition temperatures of the reacting salts themselves. Reaction time was 0.5 to 8 h and aryl methanesulfonates 3 were obtained in good yields. It must be stressed that in all the reactions with a positive outcome (Table, entries 1Ð4, 6Ð8, 10Ð15 and 17Ð21) there was also the recovery of good amounts of the o -benzenedisulfonimide ( 4 ), reusable for the preparation of the salts 1 . Conditions and yields of the studied reactions are listed in the Table. The reactions failed when a methoxy, fluoro or nitro substituent was present in the ortho position (Table, entries 5, 9 and 16). Thus, the formation of the aryl methanesulfonates 3 proceed through a D N + A N mechanism of dediazoniation 16 and that in the cases indicated in entries 5, 9 and 16 the t...

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“…After a workup identical to that described above for the preparation of 3a, the pure title compound was obtained in 76% yield (0.98 g); bp 114¡C/20 Torr (Lit. 8 bp 108¡C/25 Torr). Anal.…”

Section: P-chlorophenyl Trifluoromethanesulfonate (6c); Typical Procementioning

confidence: 99%

mentioning

confidence: 99%

A Simple Preparation of Aryl Methanesulfonates by Thermal Decomposition of Dry Arenediazonium o-Benzenedisulfonimides in Methanesulfonic Acid

Barbero¹,

Degani²,

Dughera³

et al. 1999

Synthesis

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ChemInform Abstract: REACTION OF TRIFLUOROMETHANESULFONIC ACID ANHYDRIDE WITH ARYLDIAZONIUM TETRAFLUOROBORATES

Cited by 1 publication

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A Simple Preparation of Aryl Methanesulfonates by Thermal Decomposition of Dry Arenediazonium o-Benzenedisulfonimides in Methanesulfonic Acid

A Simple Preparation of Aryl Methanesulfonates by Thermal Decomposition of Dry Arenediazonium o-Benzenedisulfonimides in Methanesulfonic Acid

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