Reactions with sulphonyl derivatives

The amides derived from sulphonic acids are called sulphonamides. They are obtained from amines by the reaction with sulphonyl chloride (R SOCl2) in pyridine. 

Copper phthalocyanine derivatives are well established as turquoise blue direct and reactive dyes for cellulosic fibres. Chlorosulphonation at the 3-position, followed by hydrolysis, yields sulphonated direct dyes such as Cl Direct Blue 86 (5.32 X = H) and Blue 87 (5.32 X = S03Na). Solubility and dyeing properties can be varied by introducing four chlorosulphonyl groups, some of which are hydrolysed and some converted to sulphonamide by reaction with ammonia or alkylamines. This approach is also the main route to reactive dyes of the copper phthalocyanine type. The reactive system Z is linked to a 3-sulphonyl site... 

A -Sulphonylation of pyrroles and indoles, using a liquidtliquid two-phase procedure [3, 48, 50-54], is superior to the traditional methods, which frequently require preformation of the heteroaryl sodium derivative, whereas A-sulphonylation of indole using a sulphonyl chloride in the presence of pyridine leads to the formation of the l,4-dihydro-4-indol-3-ylpyridine [49], The liquid liquid two-phase procedure outlined below is suitable for most A -Sulphonylation reactions with heteroaromatic compounds, but it is sometimes advisable to add a second quantity of the sulphonyl chloride during the course of the reaction [22,47]. 

Since the 4,6-acetal grouping and the glycosidic grouping (27) are stable under basic conditions, though unstable in the presence of acid, the remaining two hydroxyl groups may be suitably protected by reactions that are base catalysed. TTius (27) may be converted into the 2,3-di-O-toluene-p-sulphonyl derivative (28) by reaction with toluene-p-sulphonyl chloride in the presence of pyridine (Expt 5.119) this reaction is analogous to the formation of sulphonate esters of alcohols or phenols. 

Scheme 19). " Treatment of the amino-derivative (259) with toluene-p-sulphonyl chloride yielded the steroidal azetidinium tosylate (260), which gave the 16jS-aminopregnane (261) by reaction with lithium aluminium hydride/...

The reader may recall we discussed in Section III.A another (Reference 18, and totally independent) thermochemical study of 19, in which the heat of formation of this sulphonyl chloride, its heat of solution with ethanol and its reaction with water were all discussed. This earlier value of AHf(lq, 19) was — 94.5 + 4.5 kcal mol - in unequivocal disagreement with one we have just obtained. However, let us assume that the energetics of the reaction with water are correct because it is a simpler measurement than heats of combustion. Let us also assume that the heat of reaction of a sulphonyl chloride is independent of the choice of sulphonyl chloride. We thus derive heats of formation of —215.3 and... 

Sulphonic acids may be made from several different sulphonic acid derivatives. The synthetic utility of these preparative methods is generally limited (perhaps with the exception of the reactions involving sulphonyl halides) since many sulphonic acid derivatives are prepared starting from the sulphonic acid. Some of the more useful procedures are discussed below. 

Some functional groups that are sensitive to reaction with strong bases, like alkoxides, undergo reaction under these reaction conditions380,381. Thus 2-chloroethanesulphonyl chloride reacts with alkoxides to give the unsaturated sulphonate ester, as indicated in equation 84. Such side-reactions may be averted by reaction of the sulphonyl chloride, or fluoride, with the trimethylsilyl derivative of the alcohol382, as indicated by equation 85. The derivative may be formed under mild conditions from the alcohol. 

Other reactions forming sulphonyl halides from sulphonic acid derivatives include sulphonyl chlorides from esters with PC13647, sulphonyl fluorides from anhydrides with fluoride salts627 and sulphonyl chlorides from trimethylsilyl derivatives of sulphonic acids by reaction with dichloromethyl methyl ether648. 

In this procedure, the C-phosphorylated active methylene compound is first converted into its anion, through its reaction with KOBu BuLi, PhLi, NaH or even Et3N, and the anion is then acted upon by a sulphonyl azide the latter has been / -toluenesulphonyl azide in most recorded examples of the reaction. The first example of the adoption of this procedure to the synthesis of a phosphonic acid derivative appears to have been the conversion of triethyl phosphonoacetate into the diazo derivative (2). Since then, the procedure has been used to obtain A-substituted derivatives of the phosphonoacetamide corresponding to structure 2, but the primary amide itself undergoes further reaction to afford the C-phosphorylated 1,2,3-triazole (3)". Tetraethyl methylenebisphosphonate yields tetraethyl... 

Monocyclic Selenophens.—Selenophen has been prepared from butadiene and selenium dioxide. Selenophen-3-malonic esters have been prepared by condensation of l,4-dichlorobut-3-en-2-one with malonic esters followed by reaction with sodium selenide and cyclization. 2-(2-Selenienyl)-3,4-dicarbeth-oxyfuran has been prepared analogously to the thiophen derivative.The transient absorption spectra in the flash photolysis of selenophen have been studied. "" Butyl-lithium and phenyl-lithium attack 2,5-dimethoxyselenophen at the selenium atom, giving dibutyl selenide and diphenyl selenide, respectively, together with some dienes. " Quantitative studies of the acid- and base-catalysed hydrolyses of ethyl selenophen-2-carboxylate, of the reactions of selenophen-2-sulphonyl chloride and of 2-(chloromethyI)selenophen with aniline, and of selenophen-2-carboxaldehyde with aniline and with a phosphorus ylide have been carried out. The results were rationalized by correlation analyses with polar or electrophilic constants of heterocycles, depending on the electron demand of the side-chain. ""... 

The silyl (14) and stannyl (15) derivatives of isoprene undergo facile cycloaddition with a wide variety of dienophiles. When the latter are unsymmetrical there is a strong preference for formation of the "para" product (16). An improved synthesis of the useful prenylating agent (17) has been described. Reaction of isoprene (1) with sulphonyl chlorides gives a mixture of the... 

LAS and dialkyltetralin sulphonates are converted to their sulphonyl chlorides by reaction with phosphorus pentachloride and then to their trifluoroethyl derivatives by reaction with trifluoroethanol. These derivatives are separated on a 15 m x 0.25 mm i.d. (0.25 micron film) of DB-5 temperature programmed from 125°C (1 min) to 230°C at 5°C per min with a final hold of 5 min. Helium is the carrier gas and detection is by negative-ion chemical ionisation mass spectrometry [3]. 

Selective mesylation of methyl a-o-glucopyranoside using 3.1 moles of methane sulphonyl chloride gave predominantly the 2,4,6-tri-O-mesylate whereas under the same conditions toluene-p-sulphonyl chloride gave mainly the 2,6-di-O-tosyl derivative together with approximately equal amounts of the 2,3,6- and 2,4,6-tri-O-tosyl derivatives. The reaction with p-bromobenzene sulphonyl chloride gave an unresolved complex mixture of products. ... 

Interesting results have been published concerning the reactions of 2-O-sulphonyl derivatives of aldonolactones. The triflate (9) was converted using sodium azide in DMF into the azide (10) with overall retention of configuration, although this reaction was shown to proceed by displacement with inversion followed by epimerization of the initial azide. The C-2 epimer of (9) also gave (10) with azide in DMF, and in this case it was shown that this apparently simple inversion occurred by a sequence of epimerization to (9), displacement, and epimerization of the azide. A mixture of epimers (11), with the D-arahino-isomer predominating (7 3), was formed when 2-0-tosyl -5-deoxy-D-ribonolactone was treated with sodium azide in DMF. Treatment... 

The rates of displacement of the sulphonate group by azide ion in DMF at 110 °C have been measured for a series of toluene-p-sulphonyl and p-bromo-benzenesulphonyl derivatives of 3-0-methyl-cA/ra-inositol and 4-0-methyl-tf//< -inositol in these compounds, the arylsulphonate group was located at position 4 (or 3), and the substituents at positions 1,2, 5, and 6 were isopropylidene, acetyl, methyl, and cyclic carbonate. All of the resulting azides (except the unreactive penta-O-methyl-c/j/ra derivative) could be converted into one of two inosamine penta-acetates, viz. lL-2-amino-2-deoxy-l-0-methyl-a//o-inositol and 1d-3-amino-3-deoxy-4-0-methyl-c/ /ra-inositol penta-acetates. The results were discussed in terms of currently held views on displacement reactions with carbohydrate and related sulphonates. 

Alkyl- and aryl-sulphonyl derivatives are readily obtained by reaction of an amine with the sulphonyl chloride in aqueous alkali (Schotten-Baumann) or in the presence of pyridine. 

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