Sulfonyl hydrazides

Dithiole-3-sulfonyl hydrazides alkali metal salts,... 

This reaction, parallel with 10-77, is the standard method for the preparation of sulfonyl halides. Also used are PCI3 and SOCI2, and sulfonic acid salts can also serve as substrates. Sulfonyl bromides and iodides have been prepared from sulfonyl hydrazides (ArS02NHNH2, themselves prepared by 10-126) by treatment with bromine or iodine.Sulfonyl fluorides are generally prepared from the chlorides, by halogen exchange. 

The carbon-carbon double bond can be reduced by diimide prepared in solution in a number of ways.34 183,184 Oxidation of hydrazine with oxygen (air) or H202 in the presence of a catalytic amount of Cu(II) ion was the first method to generate and use diimide in hydrogenation.183-185 Acid-catalyzed decomposition of alkali azido-dicarboxylates,185,186 as well as thermal or base-catalyzed decomposition of aromatic sulfonyl hydrazides,183,184 are also useful methods for preparing the diimide reducing agent. 

Most 1-aminopyrroles have been synthesised from y-diketones and a substituted hydrazine. If the parent N- aminopyrrole is desired, a hydrolyzable hydrazine derivative is used, for example semicarbazide or an acyl- or sulfonyl-hydrazide (equation 182) (B-77MI30607). 

Reaction of 9-chloroacridine with aryl sulfonyl hydrazides results in aminodechlo-rination to give the corresponding A-acridinylbenzenesulfonyl hydrazides kinetic studies in methanol and DMSO have been reported.44 Reaction of electron-deficient heteroaryl chlorides with tertiary amines may proceed by quaternization and dealkylation, as shown in Scheme 3. These reactions occur under mild conditions, e.g. acetonitrile solvent at room temperature, and in THF may be accelerated by the addition of lithium chloride.45... 

Thus, gel-type polystyrene-sulfonyl-hydrazide resin 20, which originally was developed for carbonyl scavenging applications [30] can also serve as a linker for carbonyl compounds in solid phase synthesis and gives access to support-bound sulfonyl hydrazones 21 (Scheme 8)... 

The sulfonyl hydrazide D is obtained through a Mukaiyama redox condensation while consuming compounds A-C (cf. Figure 2.38). 

Fig. 1.47. Myers synthesis of atkanes from aldehydes via the sulfonylated hydrazones B and their silyl derivatives C. This procedure provides a skeletongenerating three-step synthesis of alkanes from aldehydes. In terms of Figure 1.2, the chain reaction F —> I involved is a "substitution reaction by fragmentation." (The sulfonylated hydrazide anion, which here results from the addition of R3-Li to the sulfonyl hydrazone C, does—at this reaction s temperature of-78 °C—not release toluene sulfinate. Compare the different behavior of the sulfonylated hydrazide anion C in the reaction of Figure 17.69, where a mesitylene sulfinate residue is eliminated at a temperature that is higher by 160 °C).

The method described above for the preparation of the mixture of 4-dodecylbenzenesulfonyl azides is new and based on the work of Bollinger and Hazen.5 7 Sulfonyl azides have been prepared by diazotizing substituted sulfonyl hydrazides,8 and treating sulfonyl halides in methanol-water,9 ethanol-water,10 acetone,2 5 7 or acetone-water solutions11 with aqueous or solid sodium azide,5 7 12 Use of phase transfer catalysis for the preparation of sulfonyl azides is new, simple and effective, ft avoids solvent changes and permits isolation of a hexane solution of sulfonyl azides without concentration. 

The synthesis of hybrid solution/solid-phase small arrays of 1,2,3-thiadiazoles, L20 and L21, has also been described (239). An SP strategy was first set up (Fig. 8.43) based on commercially available PS-sulfonyl hydrazide resin that was reacted with a small set of commercially available ketones (step a) to form intermediate resin-bound sulfonyl hydrazones 8.84, then submitted to cyclative cleavage to form the thiadiazoles L22 (step b) with good yields (84-99%) and GC purities (94-99%). 

A more diverse set of noncommercially available ketones was prepared in solution (Fig. 8.44) by the reaction of a Weinreb methoxymethyl amide (the 4-bromophenyl derivative 8.85 in the example) with a Grignard reagent (six representatives), purifying the crude mixtures using supported tosic acid 8.86 (step a). The solutions containing the ketones were transferred to other vessels containing PS-sulfonyl hydrazide resin, and the same reaction protocol described in Fig. 8.43 produced the final thiadiazoles... 

Dimethylamino-1 -naphthalene sulfonylaziridin (Dansylazaridin) 5-Dimethylamino-1 -naphthylamine-sulfonyl hydrazide (Dans3dhydrazide)... 

Scavenger compounds that have been patented include unsaturated fatty acids [19], sulfonyl hydrazides [20], cyclopentadienes [21], styrene-butadiene block copolymers [22], peroxides [23], and terpenes [24],... 

SYNS BENZENESULFOHYDRAZIDE BENZENESULFONIC ACID, HYDRAZIDE BENZENE-SULFONOHYDRAZIDE BENZENE-SULFONYL HYDRAZIDE BENZENESULFONYL HYDRAZINE BENZENE SULPHONOHYDRAZIDE CELOGEN BSH... 

Diimide is also formed in the thermal and base-catalyzed decomposition of benzene-, 4-methylben-zene-," 4-nitrobenzene-, and 2,4,6-triisopropylbenzene-sulfonyl hydrazide. ... 

Diimide occurs only as an unstable intermediate in the hydrolysis of azodi-carboxylic acid, in the alkaline cleavage of benzene sulfonyl hydrazide, hydroxyl-amine-O-sulfonic acid and chloramine, in the oxidation of hydrazine, and in several other organic decomposition reactions . At room temperature it readily undergoes decomposition, disproportionation, and in the presence of symmetrical multiple bonds (like the ones in olefins) hydrogen transfer reactions ... 

These derivatives (59) are generally obtained by condensation of the appropriate sulfonyl chloride (51) with an excess of hydrazine (Scheme 53). Sulfonyl hydrazides (59) react with nitrous acid (sodium nitrite-dilute acid) to form the corresponding sulfonyl azides (84), and with carbonyl compounds they yield the sulfonyl hydrazones (85) (Scheme 54). 

The thermal instability of sulfonyl hydrazides allows them to be used for the reduction of carbon-carbon double bonds the reaction depends on the in situ formation of the highly reactive diimide intermediate (86), which is a good reducing agent for alkenes. Tosylhydrazide can be used for this reduction, but triisopropylbenzenesulfonyl hydrazide (87) is preferred because it decomposes to the diimide at low temperature. In the final step, the diimide reduces the alkene to the alkane, as indicated in Scheme 56. 

Some bis (sulfonyl) hydrazides and azides are used as blowing agents in the plastics industry to obtain plastic foams. 

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