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Comptes Rendus

[Hydroxy(tosyloxy)iodo]benzene-mediated regeneration of carbonyl compounds by cleavage of carbon nitrogen double bonds
Comptes Rendus. Chimie, Volume 17 (2014) no. 9, pp. 881-889.

Résumé

[Hydroxy(tosyloxy)iodo]benzene (HTIB)-mediated regeneration of carbonyl compounds from various derivatives of carbonyl compounds of aryl and heteroaryl hydrazines containing adjacent nitrogen atoms is reported. These types of hydrazones cleaved oxidatively, giving back carbonyl compounds with HTIB, while cyclisation occurred with iodobenzene diacetate (IBD).

Métadonnées
Reçu le :
Accepté le :
Publié le :
DOI : 10.1016/j.crci.2013.10.013
Mots clés : Hypervalent iodine(III) reagents, [Hydroxy(tosyloxy)iodo]benzene (HTIB), Iodobenzene diacetate (IBD), Hydrazones, Oxidative cleavage, Regeneration of carbonyl compounds

Deepak K. Aneja 1, 2 ; Pooja Ranjan 1 ; Loveena Arora 1 ; Om Prakash 1, 3

1 Department of Chemistry, Kurukshetra University, Kurukshetra, Haryana 136119, India
2 Department of Chemistry, G. D. C. Memorial College, Bahal, Bhiwani, Haryana 127028, India
3 Manav Bharti University, Solan, Himachal Pradesh 173229, India
@article{CRCHIM_2014__17_9_881_0,
     author = {Deepak K. Aneja and Pooja Ranjan and Loveena Arora and Om Prakash},
     title = {[Hydroxy(tosyloxy)iodo]benzene-mediated regeneration of carbonyl compounds by cleavage of carbon nitrogen double bonds},
     journal = {Comptes Rendus. Chimie},
     pages = {881--889},
     publisher = {Elsevier},
     volume = {17},
     number = {9},
     year = {2014},
     doi = {10.1016/j.crci.2013.10.013},
     language = {en},
}
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JO  - Comptes Rendus. Chimie
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%A Deepak K. Aneja
%A Pooja Ranjan
%A Loveena Arora
%A Om Prakash
%T [Hydroxy(tosyloxy)iodo]benzene-mediated regeneration of carbonyl compounds by cleavage of carbon nitrogen double bonds
%J Comptes Rendus. Chimie
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Deepak K. Aneja; Pooja Ranjan; Loveena Arora; Om Prakash. [Hydroxy(tosyloxy)iodo]benzene-mediated regeneration of carbonyl compounds by cleavage of carbon nitrogen double bonds. Comptes Rendus. Chimie, Volume 17 (2014) no. 9, pp. 881-889. doi : 10.1016/j.crci.2013.10.013. https://comptes-rendus.academie-sciences.fr/chimie/articles/10.1016/j.crci.2013.10.013/

Version originale du texte intégral

[Hydroxy(tosyloxy)iodo]benzene (HTIB, PhI(OH)OTs) is a versatile hypervalent iodine(III) reagent that has numerous applications in organic synthesis [1]. Important applications of HTIB are: α-functionalization of ketones [2] ring expansion [3] ring contraction [4] ring tosyloxylation [5] α-iodination [6] preparation of iodonium salt [7] synthesis of α,β-tosyloxyketones and their conversion into pyrazoles [8] isoxazoles [9] and synthesis of various other organic compounds [10].

The regeneration of the carbonyl functionality is an important step in organic synthesis. The recovery of parent ketones and aldehydes has classically involved acid hydrolysis [11]. However, non-acidic methods are of special significance while dealing with compounds containing acid-sensitive groups [12]. So, considerable interest has been aroused in the development of mild and non-acidic methods for the cleavage of hydrazones, oximes, semicarbazones, thiosemicarbazones, etc. In this regard, a review of protection and deprotection of functional groups in organic synthesis by heterogeneous catalysis has been published by Sartori et al. [13] Though several methods have been employed for the regeneration of the carbonyl functionality, there is scope for the development of a newer and simpler methodology. The common deprotection protocols involve the use of hazardous heavy metal salts, for example mercury(II) chloride [14] and of toxic reagents such as SeO2, (PhSeO)2O, which besides being costly reagents also add to waste-disposal problems [15]. Similarly, reagents such as lead tetraacetate [16] thallium(III) nitrate [17] manganese dioxide [18] Y [19] and ZSM-5 [20] chlorochromate [21] ammonium chlorochromate adsorbed on alumina [22] iodic acid [23] N-bromo-N-benzoyl-4-toluenesulfonamide [24] vanadyl acetylacetonate [25] aqueous phosphoric acid [26] and clayfen [25] have also been utilized for the regeneration of carbonyl compounds. However, some of these methods have suffered from different drawbacks such as requirements for refluxing temperature, tedious work-up, drastic conditions, long reaction times, undesired chemical yields, and use of toxic reagents. Recently, microwave irradiation has also been developed, which is valuable from the synthetic standpoint. But extreme precautions have to be taken as these reactions are performed under microwave irradiation or ultrasonic irradiation with an oxidant [27].

Moriarty et al. [28] developed an hypervalent iodine(III)-mediated methodology for the regeneration of various carbonyl compounds from oximes using iodobenzene diacetate (IBD). Further, Barton et al. [29] proposed a method involving the iodine(III)-mediated oxidation of various hydrazone derivatives of keto esters using HTIB, IBD, and [bis(trifluoroacetoxy)iodo]benzene (BTIB), which has been reported for the regeneration of parent carbonyl compounds. Parent ketones were also regenerated from semicarbazones using IBD [30].

In connection with our ongoing programme directed towards the use of hypervalent iodine(III) compounds as unique reagents in organic synthesis, we have recently reported the simple and efficient iodine(III)-mediated cleavage of carbonyl derivatives of dehydroacetic acid (DHA) with HTIB and IBD [31]. Various derivatives of carbonyls, such as aryl/heteroaryl hydrazones, oximes, semicarbazones and thiosemicarbazones, gave the parent carbonyl back after reaction with either HTIB or IBD. Both reagents showed a similar behaviour in the cleavage of derivatives of carbonyl compounds. Encouraged by these observations, we further extended our research to study the behaviour of these two reagents towards carbonyl derivatives of other heterocyclic moieties and obtained some interesting results.

First, we carried out the oxidation of pyridylhydrazones of 4-formylpyrazoles (1a–g) with HTIB in dichloromethane (DCM) and we observed that oxidative cleavage1 occurred smoothly in this case, giving back the parent carbonyl compounds (2a–g)2. However, in our previous investigation, we had found that the same substrates when oxidised with IBD gave 1,2,4-triazole derivatives (i.e., oxidative cyclisation occurred) (Scheme 1 and Table 1) [32]. Similar results were obtained with other aromatic aldehydes (Scheme 2 and Table 2) [33].

Scheme 1
Table 1

Oxidative cleavage of carbonyl derivatives (1a-g) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
11a352a3014080
21b352b3012282
31c352c3012183
41d352d3014878
51e352e3011077
61f352f3013282
71g352g3016585
Scheme 2
Table 2

Oxidative cleavage of carbonyl derivatives (4a-f) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
14a365a60–2.6/179a76
24b365b60–6/204–205a78
34c365c6046/60a75
44d365d600/248a77
54e365e6037–3970
64f365f60198a69

a Boiling point in °C.

Encouraged by these observations, we carried out reactions with other hydrazones containing heterocyclic moieties, like quinoline [33] pyrimidine [34] phthalazine [35], etc. Interestingly, similar oxidative cleavage occurred in all cases with HTIB. It is to be mentioned that in our previous investigation oxidative cyclisation occurred with IBD in such cases (Schemes 3–7 and Tables 3–7).

Scheme 3
Scheme 4
Scheme 5
Scheme 6
Scheme 7
Table 3

Oxidative cleavage of carbonyl derivatives (7af) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
17a379a60–2.6/179a74
27b379b60–6/204–205a76
37c379c604675
47d379d600/248a77
57e379e6037–3968
67f379f60<10/198a69

a Boiling point in °C.

Table 4

Oxidative cleavage of carbonyl derivatives (10ak) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
110a3812a604670
210b3812b609–11/209–215a72
310c3812c60–6/204–205a74
410d3812d60103–10676
510e3812e6040–4377
610f3812f6072–7475
710g3812g6072–7577
810h3812h60<10/198a71
910i3812i60–21/181a62
1010j3812j608/78–81a66
1110k3812k6071–73a63

a Boiling point in °C.

Table 5

Oxidative cleavage of carbonyl derivatives (13ak) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
113a3815a60–10/181a72
213b3815b604671
313c3815c6055–5873
413d3815d60–26/179a74
513e3815e60–6/204–205a74
613f3815f600/248a76
713g3815g60103–10677
813h3815h60<10/198a69
913i3815i608/78–81a50
1013j3815j6064–6677
1113k3815k6046–4878

a Boiling point in °C.

Table 6

Oxidative cleavage of carbonyl derivatives (16ai) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
116a3818a60–6/204–205a73
216b3818b600/248e75
316c3818c6046–4876
416d3818d6046–4775
516e3818e6055–5876
616f3818f60–10/181a72
716g3818g60103–10676
816h3818h60–36/54–56a70
916i3818i6037–3968

a Boiling point in °C.

Table 7

Oxidative cleavage of carbonyl derivatives (19al) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
119a3921a60–26/179a73
219b3921b60–6/204–205a74
319c3921c604675
419d3921d6055–5874
519e3921e600/248a75
619f3921f60–10/181a72
719g3921g60<10/198a68
819h3921h60103–10676
919i3921i6034–3772
1019j3921j6064–6974
1119k3921k609–11/209–21173
1219l3921l609–12/213–1474

a Boiling point in °C.

We also carried out the reaction with pyrazolylaldehyde N-acylhydrazones (22a-g) with HTIB and it was found that in these cases also oxidative cleavage occurred with HTIB, while our previous investigation showed that oxidative cyclisation occurred with IBD (Scheme 8 and Table 8) [36].

Scheme 8
Table 8

Oxidative cleavage of carbonyl derivatives (22ag) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
122a4024a3014078
222b4024b3011080
322c4024c3014877
422d4024d3013283
522e4024e3012279
622f4024f3012180
722g4024g3016581

As expected, in the case of semicarbazones (25af), thiosemicarbazones (26af) of 4-formylpyrazoles, we observed the oxidative cleavage with both reagents i.e., HTIB and IBD. But with IBD in addition to oxidative cleavage, the formation of several products (as evident by TLC) was observed (Scheme 9 and Table 9). Similarly, in case of phenylhydrazones of 4-formylpyrazoles, oxidative cleavage occurred with both HTIB and IBD (Scheme 10 and Table 10) [37].

Scheme 9
Table 9

Oxidative cleavage of carbonyl derivatives (25af and 26af) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
125a4127a3014082
225b4127b3012181
325c4127c3012283
425d4127d3011084
525e4127e3013280
625f4127f3014885
726a4127a3014082
825b4127b3012186
926c4127c3012287
1026d4127d3011086
1126e4127e3013282
1226f4127f3014884
Scheme 10
Table 10

Oxidative cleavage of carbonyl derivatives (28af) with HTIB.

Sr. no.ReactantReferenceProductTime (in min)Melting point (°C)Yield (%)
128a4127a3014082
228b4127b3012184
328c4127c3012283
428d4127d3011085
528e4127e3013286
628f4127f3014884

Although mechanisms offering such oxidative cyclisations and oxidative cleavage with IBD and HTIB have been described in previous reports [38], there is still a need for further work to explain the different reactivity pattern of IBD and HTIB, especially the uniqueness of HTIB for CN cleavage. Therefore, on the basis of the products formed and consumption of reagent, a plausible mechanism is shown in Schemes 11–12. The first step involves an electrophilic attack of HTIB on the NH group of hydrazone with loss of p-toluenesulphonic acid, giving an unstable iodine(III) species (29d and 32c), which subsequently undergoes rearrangement, in which the –OH group attached to iodine attacks intra-molecularly to form an α-hydroxyazo intermediate (29e and 32d) and iodobenzene (it is this –OH group of HTIB (PhI(OH)OTs) that is responsible for cleavage). Another molecule of HTIB attacks the azo group to initiate the decomposition of the α-hydroxyazo intermediate (29f and 32e), giving back carbonyl compounds (31 and 34) with formation of iodobenzene, water, and salt.

Scheme 11
Scheme 12

In summary, the present study offers a significant application of HTIB in an efficient and convenient regeneration of carbonyl compounds from derivatives of carbonyl having N-containing heterocyclic systems that are known to undergo oxidative cyclisations with IBD. Semicarbazones, thiosemicarbazones and phenylhydrazones of formyl pyrazoles and other simple carbonyl compounds that do not have adjacent nitrogen atoms give carbonyl compounds back with both reagents i.e., HTIB and IBD1 [30–31]. Furthermore, the reagent HTIB is significant for the following reasons:

  • • it tolerates a variety of substrates;
  • • overoxidation of aldehydes to their carboxylic acids do not take place;
  • • the oxidative approach is ecofriendly in nature;
  • • the method only needs a very simple set-up and mild conditions.

1 Initially the reaction of hydrazone was attempted with 1.1 equiv of HTIB in dichloromethane at room temperature. The following observations were made: (a) HTIB started dissolving; (b) the colour of the reaction medium changed from yellow to reddish brown; (c) a characteristic smell of iodobenzene was observed after evaporating the solvent from the reaction mixture. All these changes indicated the occurrence of the reaction, which was supported by the monitoring the TLC of the reaction mixture. The reaction was completed in 4 h. The product obtained was found to be the parent 4-formyl pyrazole (by comparison of TLC, melting point and NMR and IR data with authentic sample) in 50% yield. To optimize the results of oxidative cleavage, the reaction of hydrazone was attempted by increasing the molar ratio of the reagent, i.e. with 2.2 equiv of HTIB in DCM at room temperature. The colour of the reaction mixture changed immediately from yellow to brown black. Usual work-up of the reaction afforded the starting carbonyl compound in 80% yield. Thus, it was found that increasing the molar ratio of HTIB not only increases the yield, but also improves the neatness of the reaction. Encouraged by these successful results, we studied the scope of the HTIB mediated oxidative cleavage with other derivatives. The effect of the solvent was also tested by using different solvents, i.e. methanol, ethanol, and acetonitrile. The reaction proceeded with equal efficacy in acetonitrile, but with poor yield in ethanol and methanol. Therefore, acetonitrile and DCM are found to be suitable solvents for the oxidative cleavage of carbonyl derivatives of various aromatic aldehydes. As expected, this procedure involving HTIB was also successful for effective cleavage of semicarbazones and thiosemicarbazones derived from simple ketones such as cyclohexanone and acetophenone etc.

2 General experimental conditions: HTIB was prepared from IBD and p-toluenesulphonic acid monohydrate in acetonitrile. IBD and all other chemicals used were purchased from commercial sources and were used without further purification. 1H NMR was recorded on a Bruker 300 MHz instrument using tetramethyl silane (TMS) as an internal standard. IR spectra were recorded with a PerkinElmer 1800 FT-IR spectrophotometer. General cleavage procedure: To a stirred suspension of hydrazone (0.000589 mol) in DCM (15 mL) was added HTIB (0.00129 mol) in portion in 10 min at room temperature in open air atmosphere. The colour of the reaction mixture changed from red/yellow to brown. The progress of the reaction mixture was monitored by TLC. Stirring was continued for 10–60 min. After completion of the reaction, the solvent was distilled off and the resulting residue was triturated with petroleum ether (boiling range 60–80 °C) to remove the iodobenzene. The product obtained was purified by recrystallization and column chromatography using petroleum ether and ethyl acetate as eluents in 60–80% yield.


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