Sulfonyl chlorides structures

Styryl sulfonyl chloride Friedel-Crafts cyclization benzo[h]thiophenes from, 4, 873 Succinic anhydrides polymers, I, 277 mass spectrometry, 4, 585 structure, 4, 552... 

Aliphatic sulfonyl chlorides that have a-hydrogen substituents, react with simple tertiary amines, such as trimethylamine, to generate sulfenes or perhaps their amine adducts 446). These species are suggested by the incorporation of one (but not more) deuterium atoms on reaction of sulfonyl chlorides with deuterated alcohols and triethylamine (447-450). A 2 1 adduct of sulfene and trimethylamine with proposed sulfonyl-sulfene structure could be isolated (451). 

Another point for structural diversification is the sulfonamide group. Imai had already shown that a wide variety of groups could be introduced at this position to optimize the reaction. Since a wide variety of sulfonyl chlorides are commercially available, a number of different types of groups could be examined (Scheme 3.34). Testing of a variety of aryl and alkyl groups on the 1,2-cyclohexanediamine backbone demonstrates that the simple methanesulfonamide 122 is clearly superior or equal to many other analogs in the cyclopropanation of cinnamyl alcohol (Table 3.11). Another concern which was directly addressed by this survey was the question of catalyst solubility. 

The most commonly employed routes for the preparation of the / -sulfatoethylsulfone group, which is the essential structural feature of vinylsulfone reactive dyes, are illustrated in Scheme 8.5. One method of synthesis involves, initially, the reduction of an aromatic sulfonyl chloride, for example with sodium sulfite, to the corresponding sulfinic acid. Subsequent condensation with either 2-chloroethanol or ethylene oxide gives the / -hydroxyethylsulfone, which is converted into its sulfate ester by treatment with concentrated sulfuric acid at 20 30 °C. An alternative route involves treatment of an aromatic thiol with 2-chloroethanol or ethylene oxide to give the /Miydroxyethylsulfonyl compound which may then be converted by oxidation into the /Miydroxyethylsulfone. 

Texas Red hydrazide is a derivative of Texas Red sulfonyl chloride made by reaction with hydrazine (Invitrogen). The result is a sulfonyl hydrazine group on the No. 5 carbon position of the lower-ring structure of sulforhodamine 101. The intense Texas Red fluorophore has a QY that is inherently higher than either the tetramethylrhodamine or Lissamine rhodamine B derivatives of the basic rhodamine molecule. Texas Red s luminescence is shifted maximally into the red region of the spectrum, and its emission peak only minimally overlaps with that of fluorescein. This makes derivatives of this fluorescent probe among the best choices of labels for use in double-staining techniques. 

Automated parallel experiments were carried out to rapidly screen and optimize the reaction conditions for ATRP of methyl methacrylate (MMA) [34]. A set of 108 different reactions was designed for this purpose. Different initiators and different metal salts have been used, namely ethyl-2-bromo-tTo-butyrate (EBIB), methyl bromo propionate (MBP), (1-bromo ethyl) benzene (BEB), and p-toluene sulfonyl chloride (TsCl), and CuBr, CuCl, CuSCN, FeBr2, and FeCl2, respectively. 2,2 -Bipyridine and its derivatives were used as ligands. The overall reaction scheme and the structure of the used reagents are shown in Scheme 2. 

Much research has been done on the synthesis of perhalogenated P-sultones. The sulfonation of acyclic fluorovinyl ethers leads to a product that is stable up to slightly above room temperature. Thermolysis decomposes the ring structure under SO2 evolution and formation of acid fluorides and perfluorocyclopropane (Eq. 78). )S-Sultones have been synthesized by addition of sulfonyl chlorides to perhalogenated ketones in the presence of triethylamine. The formation of the l-oxa-2-thiacyclobutane 2,2-dioxides appears to require an activated but sterically unhindered carbonyl group because acetone, chloroacetone, trifluoroacetophenone, and p-nitroaceto-phenone did not yield the desired products. ... 

The 4H NMR spectra of some methyl-,79-83 halo-,81 mercapto-,84 nitro-,84 and methoxybenzo[6]thiophenes,85 and of some sulfonic acids, sulfonyl chlorides, and sulfonate esters86 have been recorded. Two groups of workers87,88 have independently studied the 4H NMR spectra of a range of benzo[6]thiophene derivatives in an attempt to correlate the chemical shifts of the protons with the substituents. Such a correlation helps to assign structures to new benzo[6]thiophene derivatives, and it also throws light on the influence of substituents on the NMR parameters of heteroaromatic systems in general. 

Hydroxyalkanoic acids are easily dehydrated to either spiro or fused /3-lactones. Sulfonyl chlorides have been the traditional reagents employed for this transformation <1996S586, 2001CC753>. However, as illustrated in Equation (38) for a cyclization used as part of a synthesis of lactacystin/omuralide (see also Section 2.06.12.4), bis(oxazolidi-none) phosphinyl chloride (BOP-C1) has proven an effective agent for application in sensitive structures note also the selectivity for introduction of the fused (vs. spiro) lactone <2006JOC1220>. 

It was reported that 2,4-dimethylbenzodiazepine was mono-N-tosylated by toluene-p-sulfonyl chloride in pyridine (65JCS485), but the structure of the product has been questioned (91 C209). 

The chemical stability of PE is comparable to paraffin. It is not affected by mineral acids and alkalis. Nitric acid oxidizes PE and halogens react with it by substitution mechanisms. By chlorination in the presence of sulfur dioxide, chlorine groups and sulfonyl chloride are incorporated and an elastomer is formed. Oxidation of polyethylene which leads to structural changes can occur to a measurable extent at temperatures as low as 50 °C. Under the influence of ultraviolet light the reaction can occur at room temperature. 

Substituted imidazole-4,5-dicarbohydroxamic acids on Lossen rearrangement form 1-hydroxyxanthines. Thiazole-4,5-dicarbohydroxamic acids in their partial Lossen degradation, however, show little differentiation between the 4- and 5-position and hence mixtures of the [4,5-d] and the [5,4-d] structures (447) and (448) are formed. The isomer distribution appears to be affected by the solvent as well as by the sulfonyl chloride utilized in the reaction (68JHC331). 

We are going to do a little more than simply give the reactions that eventually made up the synthesis of dofetilide. We are going to put ourselves in the place of the chemists who invented the synthesis and try to see what led them to the reactions they chose. First, we should inspect the structure of the molecule. There are two sulfonamides, one at each end. We have seen how to make sulfonamides earlier in this chapter when saccharin was being discussed. The usual way is to react the amine with a sulfonyl chloride. In this case we shall need to react methane sulfonyl chloride (MeS02Cl or MsCl) with the aromatic amines. This is a well-known reaction and should work well here. The other functional groups—tertiary amine and alkyl aryl ether—should not interfere so no protection is needed. 

The potential antimetastatic activity of inhibitors of metalloproteinases has generated considerable work in the area as noted in the discussion of tanomastat (34). The very different stmcture of the inhibitor prinomastat (107) illustrates the considerable structural freedom that seems to exist for inhibitors of these enzymes. Displacement of halogen in 4-chloropyridine (99) by phenoxide leads to the diaryl ether (100). Reaction of intermediate 100 with chlorosulfonic acid affords the sulfonyl chloride (101). 

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