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40 Amines, Ammonium Salts, Amine N-Oxides, Haloamines, Hydroxylamines and Sulfur Analogues, and Hydrazines

DOI: 10.1055/sos-SD-040-00001

Schaumann, E.Science of Synthesis, (2009401.

General Introduction

This volume of Science of Synthesis covers the syntheses of compounds having a single bond between an sp3-hybridized carbon atom and a formally sp3-hybridized nitrogen substituent. As an aid to organization it has been split into two parts which are, respectively, Science of Synthesis, Volume 40a (Amines and Ammonium Salts) and Science of Synthesis, Volume 40b (Amine N-Oxides, Haloamines, Hydroxylamines and Sulfur Analogues, and Hydrazines). Among the product classes featured, one of the most prominent representatives is the aliphatic amines (Section 40.1); however, separate sections are devoted to propargylic (Section 40.1.2) and allylic amines (Section 40.1.3) for which special synthetic methods are available, or where special care must be taken to secure synthetic success. Similarly, compounds with more than one amino group or an additional phosphorus functionality are treated separately (Section 40.1.4), as are the obviously special small-ring amine derivatives aziridines (Section 40.1.5) and azetidines (Section 40.1.6). Furthermore, the amino group may be modified in the form of ammonium compounds or of N-ylides (ammonioalkanides; Section 40.1.7). There is also a wide range of functionalities where a parent amine structure is combined with one heteroatom. This type of compound is seen in nitroxyl radicals (nitroxides; Section 40.2), amine N-oxides (Section 40.3), N-haloamines (Section 40.4), hydroxylamines (N-hydroxyamines) in acyclic (Section 40.5) or in cyclic form (Section 40.6), and hydrazines, again in acyclic (Section 40.7) or in cyclic form (Section 40.8), as well as extended hydrazines (Section 40.9). Finally, amido derivatives of sulfur-derived acids, specifically of sulfanediol (Section 40.10), of sulfurous acid (Section 40.11), and of sulfuric acid (Section 40.12) are covered. Ammonium sulfonates, thiohydroxylamines, and aminosulfonium salts are also featured (Section 40.13). For a ready overview, these structures are compiled in Table 1.

Table 1 Classes of Amines and Amine Derivatives Covered in Volume 40

Product Class or Subclass Structure(s) Section
amino compounds 40.1
alkyl and cycloalkylamines 40.1.1
propargylic amines 40.1.2
allylic amines 40.1.3
n-nitrogen- or n-phosphorus-functionalized ­alkylamines (n 2) 40.1.4
aziridines 40.1.5
azetidines 40.1.6
ammonium compounds
nitrogen ylides
nitroxyl radicals (nitroxides) 40.2
amine N-oxides 40.3
N-haloamines 40.4
hydroxylamines 40.5
1-oxa-2-azacycloalkanes 40.6
hydrazines and hydrazinium salts 40.7
1,2-diazacycloalkanes 40.8
triazanes and tetrazanes 40.9
amido derivatives of sulfanediol 40.10
amido derivatives of sulfurous acid
N-(thio)sulfinylamines 40.11.4, 40.11.5
N,N-dialkylsulfur diimides 40.11.6
N-alkylsulfamic acids and derivatives 40.12
ammoniumsulfonates, thiohydroxylamines, and aminosulfonium salts 40.13

For a product class to be included in Volume 40, the hierarchy of Science of Synthesis requires that the carbon in the CN bond is sp3 hybridized. The chemistry of ynamines 1 (X=CR3) is covered in Science of Synthesis, Vol. 24 [Three CarbonHeteroatom Bonds: Ketene Acetals and YneX Compounds (Section] and the chemistry of cyanamides 1 (X=N), where an sp-hybridized carbon is bonded to the nitrogen, is described in Vol. 18 [Four CarbonHeteroatom Bonds: XCX, X=C=X, X2C=X, CX4 (Section 18.1.4)]. If the carbon is sp2 hybridized, as in general structure 2, the products can be enamines 2 (X=CR4R5) {see Science of Synthesis, Vol. 33 [EneX Compounds (X=S, Se, Te, N, P) (Section 33.4.633.4.6)]} or amide-type derivatives 2 (X=O or heteroanalogues), covered as carbonic acid derivatives in Science of Synthesis, Vol. 18 (Four CarbonHeteroatom Bonds: XCX, X=C=X, X2C=X, CX4), and as carboxylic acid amides in Vol. 21 (Three CarbonHeteroatom Bonds: Amides and Derivatives; Peptides; Lactams), and as their heteroanalogues in Vol. 22 (Three CarbonHeteroatom Bonds: Thio-, Seleno-, and Tellurocarboxylic Acids and Derivatives; Imidic Acids and Derivatives; Ortho Acid Derivatives). Compounds 3 with an NR1 unit as a member of a heteroaromatic ring (n 1) are the subject of Category 2 (Hetarenes and Related Ring Systems; Vols. 917).

Aliphatic nitrogen compounds 4 with a double bond to another heteroatom are the subject of Science of Synthesis, Vol. 41 (Nitro, Nitroso, Azo, Azoxy, and Diazonium Compounds, Azides, Triazenes, and Tetrazenes) as are nitrogen functionalities with two other heteroatoms on the nitrogen as in 5 and 6. Compounds 6 (nitroso acetals) formally encompass derivatives 7 (X=Y=NR12). However, from another point of view, compounds 7 are extended hydrazines (triazanes when n=1, tetrazanes when n=2) and therefore are described here in Section 40.9

Based on the priority rules of Science of Synthesis, sp3 hybridization of the carbon in the CN bond is not a sufficient criterion for inclusion in the present volume; in addition, no other heteroatom on the substituted carbon is allowed. Similarly, if another functional group of higher priority is present on the neighboring carbon, the synthesis is covered at the location of that group. Finally, compounds with nitrogenmetal bonds are covered in Category 1 (Organometallics; Vols. 18). An overview of the location of the different types of formal amino derivatives is given in Table 2. In any case, to get the full information that is available in Science of Synthesis on amino derivatives, a substructure search in the electronic version is recommended.

Table 2 Amino Group Containing Structural Units Covered Elsewhere in Science of Synthesis

Name Structure(s) Volume Section
aminoboranes, boraneamine complexes 6 (Boron Compounds) 6.1.15
aminealuminate ­complexes LiAlH4-n(NR1R2)n, LiAlH4NR1R2R3 7 [Compounds of Groups 13 and 2 (Al, Ga, In, Tl, BeBa)]
alkylaluminium amides 7.1.7
magnesium amides (R1R2N)2Mg 7.6.14
lithium amides R1R2NLi 8a [Compounds of Group 1 (LiCs)] 8.1.6
α-lithioamines 8.1.21
potassium amides R1R2NK 8b [Compounds of Group 1 (LiCs)], 8.3.6
orthocarbamic acid triesters 18 (Four CarbonHeteroatom Bonds: XCX, X=C=X, X2C=X, CX4) 18.16.3
orthocarbonic acid ­diester diamides 18.16.6
alkoxytriaminomethanes 18.16.9
trithioorthocarbamic triesters 18.16.11
dithioorthocarbonic acid diester diamides 18.16.13
organosulfanyl-, and organoselanyltriaminomethanes 18.16.15
orthocarbonic acid ­tetraamides 18.16.17
2-aminoalkanoic acids 20a (Three CarbonHeteroatom Bonds: Acid Halides; Carboxylic Acids and Acid Salts) 20.2.7
3-aminoalkanoic acids
2-aminoalkanoic acid ­esters 20b [Three CarbonHeteroatom Bonds: Esters and Lactones; Peroxy Acids and R(CO)OX Compounds; R(CO)X, X=S, Se, Te] 20.5.10
3-aminoalkanoic acid ­esters
α,N-substituted ­alkanamides 21 (Three CarbonHeteroatom Bonds: Amides and Derivatives; Peptides; Lactams) 21.5.3
β,N-substituted ­alkanamides 21.7.5
ortho amides 22 (Three CarbonHeteroatom Bonds: Thio-, Seleno, and Tellurocarboxylic Acids and Derivatives; ­Imidic Acids and Derivatives; Ortho Acid Derivatives) 22.7.6
2-aminoaldehydes 25 (Aldehydes) 25.4.3
α-amino ketones 26 (Ketones) 26.6.8
N/X-acetals 30 (Acetals: O/N, S/S, S/N, and N/N and Higher Heteroatom Analogues) 30.1.1, 30.1.2, 30.4, 30.5.4, 30.5.5, 30.6, 30.7.1
diaryl(aza)sulfonium salts 31a [AreneX (X=Hal, O, S, Se,Te)]
alkyl(aryl)(aza)sulfonium salts
diaza(aryl)sulfonium salts
arylamines 31b [AreneX (X=N, P)] 31.28
arylammonium salts 31.29
N-haloarylamines 31.32
N-arylhydroxylamines 31.33
arylhydrazines 31.34
cyclic arylamines 31.38
β-fluoroamines 34 (Fluorine) 34.10
β-chloro-, β-bromo-, and β-iodoamines 35 (Chlorine, Bromine, and Iodine),,,,,
β-amino alcohols 36 (Alcohols),,,
γ-amino alcohols
β-amino thiols 39 (Sulfur, Selenium, and Tellurium),