Primary amine sulfonamide

Other catalysts such as those depicted in Scheme 2.10 have also been developed following the same concept. In particular, primary amine-sulfonamides 27a and 27b, in which the sulfonamide N-H group plays the role of the hydrogen-donor group, have been successfully applied to the reaction of... 

Scheme 2.10 Enantioselective Michael addition of ketones to nitroalkenes catalyzed by primary amine-sulfonamide catalysts 27a-b and by 9-epi amino cinchona alkaloid 28a.

Recently, by using a primary amine sulfonamide/benzoic acid salt, Liang and Ye [57] developed an unprecedented example in the asymmetric Michael addition of ketones to maleimides (Scheme 5.30). The reaction is quite general, and it provides the corresponding Michael adducts in good to excellent yields with excellent enantioselectivities. 

Recently, carbohydrates and steroids derived primary-thioureas catalysts 69 and 70 have been reported for the Michael reactions of aryl ketones and aryl nitrolefins with high yield and enantioselectivity (Scheme 5.20)[38]. Primary amine-sulfonamide catalysts can also be applied to similar reactions with good to high... 

NaAlH2(0CH2CH20CH3)2, benzene or toluene, reflux, 20 h, 65-75% yield. Note that LiAlH4 does not cleave sulfonamides of primary amines those from secondary amines must be heated to 120°. 

The treatment of sulfonyl chlorides with ammonia or amines is the usual way of preparing sulfonamides. Primary amines give N-alkyl sulfonamides, and secondary amines give N,N-dialkyl sulfonamides. The reaction is the basis of the Hinsberg test for distinguishing between primary, secondary, and tertiary amines. N-Alkyl sulfonamides, having an acidic hydrogen, are soluble in alkali, while N,N-dialkyl sulfon-... 

Treatment with sodium hypochlorite or hypobromite converts primary amines into N-halo- or N,N-dihaloamines. Secondary amines can be converted to N-halo secondary amines. Similar reactions can be carried out on unsubstituted and N-substituted amides and on sulfonamides. With unsubstituted amides the N-halo-gen product is seldom isolated but usually rearranges (see 18-13) however, N-halo-N-alkyl amides and N-halo imides are quite stable. The important reagent NBS is made in this manner. N-Halogenation has also been accomplished with other reagents, (e.g., sodium bromite NaBr02) benzyltrimethylammonium tribromide (PhCH2NMe3 Br3"), and NCS. The mechanisms of these reactions involve attack by a positive halogen and are probably similar to those of 12-47 and 12-49.N-Fluorination can be accomplished by direct treatment of amines °° or... 

Mg or Ca in MeOH, " baker s yeast, Sm/l2, LiMe2NBH3, and tin complexes prepared from SnCl2 or Sn(SR)2. This reaction, combined with RX —+ RN3 (10-65), is an important way of converting alkyl halides RX to primary amines RNH2 in some cases the two procedures have been combined into one laboratory step. Sulfonyl azides (RSO2N3) have been reduced to sulfonamides (RSO2NH2) by irradiation in isopropyl alcohol and with NaH. ... 

Diazotization of the primary amine [3, 17] followed by coupling with a-naphthol or N-(l-naphthyl)-ethylenediamine. Sulfonamides also react [18]. 

The addic compounds used can be compounds with N-H bonds (aromatic primary amines [1], azole heterocycles [2-5], sulfonamides [6]), or enoHzable compounds with activated C-H bonds [7,8]. 

The chlorination of the antibacterial sulfonamide sulfamethoxazole was initiated by N-chlorination of the primary amine. Further reaction of the A,A-dichlorinated compound resulted in the final production of 3-amino-5-methyloxazole and 1,4-benzoquinone-imine (Dodd and Huang 2004). 

Aminolyses of the imidazolides of aromatic sulfonic acids require prolonged heating with a primary amine at temperatures above 100 °C in a sealed tube to generate sulfonamides in good yield. 

The polymer-supported 5-chloromethyl-l,2,4-oxadiazole 162 undergoes easy reaction with primary amines to give the 5-aminomethyl oxadiazoles 163, which serve as excellent substrates for the synthesis of amides or sulfonamides 164 (Scheme 21 - yields not reported) <1999TL8547>. 

The instability of primary nitramines in acidic solution means that the nitration of the parent amine with nitric acid or its mixtures is not a feasible route to these compounds. The hydrolysis of secondary nitramides is probably the single most important route to primary nitramines. Accordingly, primary nitramines are often prepared by an indirect four step route (1) acylation of a primary amine to an amide, (2) A-nitration to a secondary nitramide, (3) hydrolysis or ammonolysis with aqueous base and (4) subsequent acidification to release the free nitramine (Equation 5.17). Substrates used in these reactions include sulfonamides, carbamates (urethanes), ureas and carboxylic acid amides like acetamides and formamides etc. The nitration of amides and related compounds has been discussed in Section 5.5. 

Amines may also behave as nucleophiles (Lewis bases). Primary amines are stronger nucleophiles than secondary amines, which, in turn, are stronger nucleophiles than tertiary amines. As nucleophiles, amines attack acid chlorides to form amides. Later in this chapter you see that they re important in the formation of sulfonamides. 

Primary amines react to form an N-substituted sulfonamide (as shown in Figure 13-37). 

Synthesis of the sulfonamides is accomplished with the camphorsulfonic acid chloride in a 1 1 ratio with the chiral primary amine in pyridine (2 h, 60 °C). 

A method for the determination of the absolute configuration of chiral primary amines of type 1 has been developed on this basis251. The amines 1 are converted via sulfonamides 2 into... 

Ethylene dinitramines [(N02)NHCH2CH2NH(N02)] and ethylene bis-sulfonamides condense with formaldehyde and primary amines or hydrazines to give triazepanes, e.g. (496) (7. TOC3846). 

Pyrylium cations form pyridines with ammonia and pyridinium salts with primary amines (B-82MI 505-02). For example, 2,4,6-triphenylpyrylium cation (261 Z=0) yields 2,4,6-triphenylpyridine with ammonia, the corresponding 1-methylpyridinium salt with methylamine, and pyridine 1-arylimines with phenylhydrazine. Xanthylium ions (210), where ring opening cannot readily occur, form adducts (262) with ammonia, amines, amides, ureas, sulfonamides and imides. Similar adducts (e.g. 263) are formed by benzo[( ]pyrylium ions. 

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