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A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, Arsenic, Antimony and Bismuth

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A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, Arsenic, Antimony and Bismuth J. Chem. Chem. Eng. 9 (2015) 90-100 doi: 10.17265/1934-7375/2015.02.002 D DAVID PUBLISHING A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, Arsenic, Antimony and Bismuth Aibassov Yerkin Zhakenovich*, Yemelyanova Valentina Stepanovna, Shakieva Tatyana Vladimirovna, Aibassov Gizatulla, Abenov Bakhyt and Bulenbayev Maksat Research Institute of New Chemical Technologies and Materials, Kazakh National University Al-Farabi, Almaty 005012, Kazakhstan Abstract: We discovered a new approach modification Bamberger, Barton, Beckmann, Wallach, Gabriel, Hofmann, Hofmann A.W. Martius, Dimroth, Semmler-Wolff-Schroeter, Sus, Claisen, Newman-Kwart, Orton, Pistschimuka, Robev, Smiles, Sawdey, Sommelet, Stevens, Tiemann, Fischer-Hepp, Chapman, Chattaway, Schonberg, Stieglitz Rearrangements with of phosphorous, arsine, stibine and bismuthine in organometallic chemistry. The authors have proposed a new mechanism for possible reactions. Key words: Rearrangements, organic compounds of arsenic, antimony, bismuth. 1. Introduction R(NO2)C6H3-NHR' (1) where, R = H, CH3, NO2, Cl, Br; R' = H, CH3. Have now been discovered a lot of new reactions of It is known that Bamberger arylhydroxilamins in organometallic chemistry of phosphorus, arsenic, n-aminophenols in the presence of mineral acids antimony and bismuth. The resulting novel (H2SO4) [3]: compounds have potential biologically active R-C6H4-NHOH → [R-C6H4-NHO+H2 + H2O → substances and can be used in medicine. R(HO)C6H3=NH] → R(HO)C6H4-NH2 (2) We were interested to analyze the classical It is known that Barton photochemical rearrangement in organic chemistry and try to modify rearrangement of nitrites in nitroso compounds by them, and to expand the scope of their application. intramolecular exchange nitroso on hydrogen bonded In this paper the 26 classical rearrangements in to γ-carbon atom, followed by isomerization to oximes, order to study the possibility of expanding and or dimerization [4, 5]: modifying them by replacing the nitrogen atoms to NO2-C4H8-CH(H)-C3H6CH3 + hν → phosphorus, arsenic, antimony and bismuth. O*-C4H8-CH(H)-C3H6CH3 + *NO → 2. Theory HO-C4H8-C*H-C3H6CH3 + *NO → HO-C4H8-CH(NO)-C3H6CH3 → Dimer + It is known that Bamberger Rearrangement HO-C4H8-C(=NOH)-C3H6CH3 (3) arilnitramines in o-nitroanilines by acids (H2SO4, Reacting a aliphatic, aliphatic-aromatic and CH3COOH, HCOOH) [1, 2]: alicyclic compounds and compounds containing R-C6H4-NR'-NO2 → R-C6H4-N+HR'-NO2 → + + various functional groups (Hal, OR and et.): [R-C6H4-N HR'-O-NO → R-C6H3=N HR'(NO2)] → C6H5-(CH2)4ONO + hν → [C6H5-CH(NO)-(CH2)2CH2OH]2 (4) *Corresponding author: Aibassov Yerkin Zhakenovich, (CH2)3CHONO + hν → ONCH2(CH2)2CHO (5) Professor, research field: metalorganic chemistry of uranium, As, Sb and Bi. E-mail: [email protected]. A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, 91 Arsenic, Antimony and Bismuth The reaction is used in steroid chemistry, as they Rearrangement following: allow to introduce functional groups in the molecule inactive space. It is known that Beckmann Rearrangement An (7) acid-induced rearrangement of oximes to give amides [6-9]: Oximes generally have a high barrier to inversion, (6) and accordingly this reaction is envisioned to proceed by protonation of the oxime hydroxyl, followed by This reaction is related to the Hofmann and migration of the alkyl substituent “trans” to nitrogen. Schmidt Reactions and the Curtius Rearrangement, in The N-O bond is simultaneously cleaved with the that an electropositive nitrogen is formed that initiates expulsion of water, so that formation of a free nitrene an alkyl migration. Mechanism of the Beckmann is avoided. (8) It is known that Wallach rearrangement where, R = OR', n-C6H4R" (R" = H, CH3, OCH3, Cl, azoxybenzenes in p-oksiazobenzols when heated by Br, NO2); R' = CH3, C2H5. the action of sulfuric acid [10-15]: Similarly (N-izathinyl) acetic ester derivative H-C6H4-N=N(O)-C6H5 → HO-C6H4-N=N-C6H5 (9) rearranges to 3,4-dioksihinoline: Electron-donating substituents, and the substituents C6H4C(=O)C(=O)NCH2COOC2H5 → cause steric hindrance, prevent reaction. C9H4N(OH)(OH)COOC2H5 (11) Known that Gabriel rearrangement It is believed that during the reaction there is an N-carboxymethyl- and N-phenaculphtalimids in a opening of the imide ring and rearrangement imide substituted 1,4-dioxiizohinolins under the influence of anion in a carbanion, followed by intramolecular sodium alcoholate RONa [16-19]: Dieckmann condensation. C6H4(CO)2NCH2COR → The starting compounds are prepared by alkylation C6H4(COOR')-CONHCH2COR → of phthalimide potassium halocarboxylic acids or C9H4N(OH)(OH)COR (10) esters phenylacylhalogenids. 92 A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, Arsenic, Antimony and Bismuth It is known that the Hofmann rearrangement is the than the secondary. If R is a branched chain, in the organic reaction of a primary amide to a primary amine process of the rearrangement is also isomerization with one fewer carbon atom [20-25]. radical, e.g.: C6H5NH(CH2)2CH(CH3)2 → n-(CH3)3CCH2-C6H4NH2 (16) (12) Modification Reilly-Hickinbottom-rearrangement in the presence of metal halides (ZnCl2, CdCl2): The reaction of bromine with sodium hydroxide C6H5NHR·HX → R-C6H4NH2·HX (17) forms sodiuum hypobromite in situ, which transforms Known that the Dimroth Isomerization of the primary amide into an intermediate isocyanate via a 1-substituted-1,2-dihydro-2-iminopirimidinov under formation of a nitrene. The intermediate isocyanate is the action of bases in a 2-substituted hydrolyzed to a primary amine, giving off carbon aminopyrimidines (amidine rearrangement) [30]: dioxide. R'-C4H2NR=NH → R'-C4H2N2-NHR (18) where, R = Alk, CH2COOC2H5; R' = Alk, Hal, NO2, (CH3)2N, CONH2. Electron-withdrawing groups on the pyrimidine ring accelerate rearrangement. The reaction rate increases in the number of substituents R (the highest (13) rate of reaction at the methyl radical): Several reagents can substitute for bromine. Lead CH3 < C2H5 < C4H9 < C7H15 < CH2CH=CH2 < tetraacetate, N-brromosuccinimide, CH2C6H5 < CH2C6H4NO2-n. (bis(trifluoroacetoxy)iodo) benzene, and DBU In non-aqueous media rearrangement slows down. (1,8-diazabicyclo[5.4.0]undec-7-ene) can effect a Rearrangement is general and is observed in a number Hofmann rearrangement. In the following example, the of heterocyclic systems, especially for triazines, intermediate isocyanate is trapped by methanol, tetrazoles, thiadiazoles, adenines. forming a carbamate. It is known that the Semmler-Wolff-Schroeter Rearrangement of oximes α, β-Unsaturated alicyclic (14) ketones in aromatic amines under the action of a mixture of the Beckmann ((CH3CO)2 + CH3COOH, o In a similar fashion, the intermediate isocyanate can HCl, 100 C) [31-40]: be trapped by tert-butyl alcohol, yielding the R-C6H8=NOH + (CH3CO)2 + CH3COOH → tert-butoxycarbonyl (Boc)-protected amine. [R-C6H8=NOCOCH3 → Known that the Hofmann A.W. Martius Thermal R-C6H8=N+HOCOCH3] → rearrangement of N-alkylanilines hydrochlorides in R-C6H4-NH2 (19) C-alkylanilines [26-29]: where, R = H, Alk, pyridyl. + - C6H5NHR·HX → [C6H5NH2 + R + X ] → This reaction takes disubstituted ketones oximes R-C6H4NH2·HX (15) and ketones outside the fused system (α-tetralone, where, X = Cl, Br, J. 1-ketotetragidrofenantren). This reaction also come N, N-dialkylanilines. Known that the Sus photochemical rearrangement Mainly formed of para-isomers. The migration of of o-hinondiazidov in ketenes, accompanied by primary alkyl groups occurs at a higher temperature contraction cycle [41-44]: A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, 93 Arsenic, Antimony and Bismuth + - - + C10H6(=O)=N =N ↔ C10H6(O )-N =N + hν → Ar-O-C(=S)-NR2 → Ar-S-C(=O)-NR2 (28) + - + - [C10H6 (O ) C10H6 (O )] → C9H6=C=O + H2O → Alkaline hydrolysis of S-aryltiocarbamats leads to C9H6-COOH (20) the corresponding thiols. The reaction is a convenient method of obtaining a The reaction is used as one of the steps of recovery number of acids cyclopentadiene. of phenols, which is not suitable for the direct Regrouping undergo various cyclic α-diazo ketones hydrogenation: (alicyclic, heterocyclic compounds of terpene series). Ar-OH + COS + NH(C2H5)2 → The starting o-hinondiazidy diazotization receive Ar-O-CSN(C2H5)2 → appropriate o-aminohinons. Ar-S-CON(C2H5)2 + KOH → Known that the Claisen Thermal rearrangement of Ar-SH + H2 → ArH (29) allyl ethers of phenols or enols in the isomeric C-allyl It is known that the Orton Rearrangement of derivatives [45-52]: N-halogeno-N-atsilarilaminov in o- and -CH=CH-O-CH2CH=CHR → n-galogenarilamidy by acids (CH3COOH) [56-58]: [O=CHCH2-CHR-CH=CH2] → R-C6H4-N(X)COR'+ HX → HO-CH=CH-CH(R)CH=CH2 (21) [2R-C6H4-NHCOR'+ Х2] → where, R = H, Alk. C6H5. R-C6H3(NHCOR")(п-X) + Examples of reactions: R-C6H3(NHCOR')(o-X) (30) R-C6H4-O-CH2CH=CHR' → In the resulting mixture prevails para-isomer. R-C6H3(OH)CHR'CH=CH2 (22) Regrouping and goes for naphthalene derivatives. CH2=CH-O-CH2CH=CH2 → Regrouping can take place in non-aqueous media CH2=CHCH2-CH2CHO (23) by the action of ClCH2COOH, C6H5CH2COOH, o- or Similar rearrangement observed in heterocycles such: m-O2NC6H4COOH: C6H4ZN=C-OCH2CH=CH2 → C6H5NXCOR + R'COOH → C6H4ZN(-CH2-CH=CH2)C=O (24) [C6H5NHCOR + R'COOX] → where, Z = O, S. X-C6H5NHCOR + R'COOH (31) This reaction is widely used in the synthesis of Known that the Pistschimuka the conversion of natural compounds, such as essential oils. aromatic amines to azo compounds by the action of Like allyl ether enamines rearrange to form imines selenium (or sulfur) and merkuratsetamide [59, 60]: (amino-Claisen rearrangement - amino-Claisen): 2ArNH2 + Se + (CH3CONH)2Hg → CH2=CH-CH2-NR-CH=C(R)-CH3 → Ar-N=N-Ar (32) CH2=CH-CH2-C(R)(CH3)-CH=NR (25) where, Ar = C6H4R, R = H, CH3, OCH3, NO2, Cl, where, R = Alk, C6H5. N(CH3)2. Undergo a similar rearrangement unsaturated Merkuracetamide serves to bind the liberated thioesters (thio-Claisen rearrangement - thio-Claisen): hydrogen selenide (or hydrogen sulphide).
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