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Hydroxylamine-O -Sulfonic Acid — a Versatile Synthetic Reagent

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Hydroxylamine-O -Sulfonic Acid — a Versatile Synthetic Reagent Hydroxylamine-O -sulfonic acid — a versatile synthetic reagent Raymond G. Wallacef School of Chemistry Brunei University Uxbridge, Middlesex UBS 3PH Great Britain imidazoli nones and related derivatives are time to these various modes of reaction. discussed in the review. Many of these The uses of HOSA as a reagent are organiz­ preparations can be carried out in high ed below according to the different syn­ yield, thetic transformations that it can bring about. Hydroxylamine-Osulfonic acid, NHj-OSOjH (abbreviated to HOSA in Probably by far the most well known this article) has become in recent years and explored reactions of HOSA are commercially available. Although much animation reactions, illustrating elec­ fruitful chemistry has been carried out us­ trophilic attack by HOSA, with amination ing HOSA, to this author's knowledge, on nitrogen being the most important, there has been no systematic review in although a significant number of English* of its use as a synthetic reagent. It animations on both carbon and sulfur have is a chemically interesting compound been reported, Amination on phosphorus because of the ability of the nitrogen center also occurs. to act in the role of both nucleophile and AMINATION electrophile, dependent on circumstances, Synopsis (a) At a nitrogen atom and thus it has proved to be a reagent of Hydroxylamine-0-sulfonic acid (0 Preparation of mono- and di- great synthetic versatility. (HOSA) has only recently become widely substituted hydrazines and trisubstituied commercially available despite the fact that H,N-Nu hydrazinium salts it has proved to be a valuable synthetic reagent in preparative organic chemistry. (as an electrophilic X Ji-H • ^N-NH, Unfortunately, however, information center) | Nu regarding the use of HOSA in organic syn­ 0 \ l* thesis has remained scattered in the -N • -N-NH H,NOS-OH a literature, and it is to focus attention on the ' ii versatility and potential of this reagent that 0 Monosubstituted hydrazines can be this information has been brought together E prepared in yields of the order of 50% by now in the form of a short review article. 1 treatment of a primary amine with HOSA (as a nucleophilic • in aqueous solution in the presence of base Important among the areas of applica­ center) Q (eq. I),2_s Similarly, secondary amines tion of HOSA are aminationand reductive E-N-0-3-OH react to give 1,1-disubstituted hydrazines dea mi nation reactions, nitrile and oxime M (eq. 2)S* formation, and the preparation of amides H O and diazo compounds. These and other Besides being directly involved in reac­ An alternative route for mono- or di- reactions, including the use of HOSA for tions, it may serve as an in xiiu source of substituted hydrazines uses an aqueous the synthesis of heterocycles such as ox- other chemical entities [e.g., imene) which solution of the amine and a ketone, or the aziridines, diaziridines, pyrroles, isothi- then undergo reaction with a given sub­ strate. Reference will be made from lime to +On secondment from the Cancer Research Cam­ azoles, benzisoxazoles, benzodiazepines, paign's Gray Laboratory, Mounl Vernon Hospilat, isothiazolo- and pyrazolopyridines, and 'For a short review in Japanese see ref. I. Northwood, Middlesex I1A6 2RN. 1980 by Aldrich Chemical Company, Inc. Aldrichimica Ada. Vol 13. No. I, 1980 3 corresponding SchhTs base, instead of !he amine alone and involves diaziridine ring RNH HOSA/KOH/HjO ^ formation (vide infra) which avoids the use RNHNHj R=CH3 49-53% (eq. 1) * 70"/10 m in " of a considerable excess of amine to sup­ R=C6H5 81-68% press further reaction of the hydrazine product and has additional advantages (for HOSA/KOH/H,0 a discussion see reference 6 and references (n-C^jNH 75V40m-^> (rt-C^NNH, 34% («,. 2) ciled therein). I.lj-Trisubstituied hydrazinium salts are formed when ternary amines are (CH3)3N |i)HOS^KOH^OM > (cH^NHi(- 85% (eq.3) treated with HOSA under basic conditions in aqueous or alcoholic media{eqs.3,4).'1^' (ii) Masked hydrazines - amination on the nitrogen heteroatom of nitrogen CH3 HOSA/EtOH heterocycies (CH^NfCHjjOH —£ HO(CH2)2-N*-NH2 SO; % (eq. 4) rellux/5mlfi 66 Ql-NH, CH, J2 \\ + NH, NNH, 26% (eq. 5) Many nitrogen helerocycles can be o OVIhr 0 aminated on nitrogen using HOSA. These include azetidine,"pyridine,4'5 quinoline,4S pyridazine,9 pyrimidine,' pyrazine,^ 10 t! IJIi (i) HOSA/H;O/90°/30min tetrazole, indole, "> benzimidazole, (ii) KjCOj/room lemp. ec 6 triazine,'4 benzoxazole," and purine12-'*' (iii) HI/-20°/1hr Nf .- 63-72% < "- ' ring systems (eqs. 5-16). (The pyrimidine NHj ring system, however, will often undergo ring opening and rearrangement reactions as alternative reaction pathways:9 a specific example of this is given under mis­ (t) HOSA/KOH/H;0/eO°/45 min cellaneous reactions.) Here, as in the syn­ (ii) Hl/-10°/lhr thesis of the simple hydrazines, the ni­ OH trogen of the HOSA acts as an elect rophilic center in the reaction. In the case of the 1-aminopyridinium (i) HOSA/KOH/H,O/70°/4hr (eq. 8) 4 cation, -' 1-aminoindole." and 1,2-di- N ^J-rH <'» HI N'' "-n3 aminobenzimidazole" especially, the 7 ,- R=CH3 56% method constitutes an important NH; ' R=CH30 50% preparative procedure since the reaction either fails with other reagents (pyridine) or N' the HOSA synthesis provides a more HOSA/NaOH straightforward route to the compounds in question (indole, benzimidazole). I- p" R-H, R"=NH2 Aminobenzotriazole14 forms a convenient benzyne precursor. •>• 7fKi (Hi) Preparation of 2-tetrazenes (i) HOSA/KOH/H3O/70°/dhr (II) HI (VH • (WNV) <«^N i ' R,=Ri=H 34% NHj R,=Ra=CH3 55% Piperidine and pipercolines react with HOSA in aqueous solution, in the presence M R NH "I) *\ HOSA/Na;CQ3(pH 7-8)/H,0 "Tj N' * of sodium hydroxide, to give 1,1,4,4-tetra- ill sfi 70-75° 20min/at retlux, 20-30min ~ [^ ^(Jj substituted 2-tetrazenes (eq. 17).I! Pre­ sumably, the simple hydrazine is initially 35% (eq.11) formed and is subsequently oxidized to the tetrazene. "r=i (b) At a carbon atom R=n-C3H7 26% HOSA will aminate on aliphatic, aromatic and heterocyclic carbon atoms under a variety of conditions. HOSA/KOH/DMF . (i) Aliphatic carbon ! I ; room temp./1hr X (eq. 12) J,u R'=R2=H 96% -C-H -C-NH2 nz ™ R<=CHiC6H5, Ri=H 84% 4 Atdrhhinm-a Ada. Vol. li, No. I. 1980 One of the most successful of these procedures is the elegant one-step synthesis HOSA/KOH/H,0 ^ of a-amino acids from carboxylic acids. room temp. " {eq. 13) The acid is lithiated in a mixed solvent :D> system and afterwards treated with HOSA R,=H, =H 76% (eq. 18)IK to give the a-amino acid. HOSA will also aminate active methylene com­ pounds as is demonstrated in the synthesis N •I N of substituted pyrroles" from /3-keto esters HOSA/KOH/HsO (^ (eq. 14) and ,8-diketones. 60° > cK N," NH2 [iff Aromatic carbon C l ~» )>" NH, HOSA >< (no details) (eq. 15) Two main methods have been employed i to bring about direct animation in NH H 2 aromatic systems using HOSA. In both cases the yields tend to be on the low side. The first employs aluminum chloride as a catalyst and has been fairly extensively T || V HQSA/pH >7- investigated by Keller™ and Kovacic.2' There appears to be a number of points of (eq. 16) variance between the work of the two authors. The precise animating species is OHOO-H IOH not known. Examples from both authors' work are given below (eqs. I9.20).-"-3' almost quantitative "Note: pH 2-4 gives C-8 ami nation The second method is a homolytic animation procedure developed by Minisci R2 p» pi pi and his co-workers," whereby what is f* ,R' thought to beaprotonated amino radical is R'-ZfJ-H HOSA/NaOH/H^ tf/"""^-^-/"^. (eq. 17) generated in a redox system (H,N- 60-70" /2hr •OSO,H/Fe") at room temperature and this then attacks an aromatic substrate. R1=R2=R3^H 18% Yields of between 10 and 40% of mono- aminated product are reported {eq. 21). (In RCH^CH •-iN^PQ./HMPT/THF-he-ane > RCHUCOiU HOSA ^ many instances the yields are quantitative -15°/2hr with respect to the aromatic substrate ac­ (eq. 18) tually consumed.) In certain cases the reac­ RCH(NH2)CO,H R=C6H5 83% tion shows a degree of stereospecificity. A third method,21 from the very recent CH, literature, is based on H.C. Brown's HOSA/AICI, H,N 21% (eq. 19) procedure for the conversion of alkenes via 95-105°/30min CH, thcorganoborane to aliphatic amines (vide infra). If an ary] orgaiioboraue is sub­ stituted for the alkyl borane in the reaction (the paper gives triphenyiborane as an ex­ ample - prepared from phenylmagnesium HOSA/AICI, bromide and boron trifluoride) an aryl- 50% (eq. 20) amine is produced (eq. 22). The disadvan­ 100-105° /30m in & tage of the method is that, unlike trialkyl boranes. which utilize two of the three alkyl groups in amine formation, triphenyi­ borane uses only one phenyl group and OCHj thus the overall yield with regard to anima­ tion on the aromatic ring is not high, HOSA/FegSOj/MeOH NHj (eq. 21) foom temp./15min 34% (iitf Heterocyclic carbon (with respect to HOSA) )C-U Jc-NHj HOSA/diglyme Certain heterocyeles will react with M^B CSHSNH, 35% (eq. 22) 100"/24hr HOSA to give a C-.substituted amino derivative. For instance. 1.3-dimethyl- Akfrwhimiea Aaa. Vol.
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