Functionally-substituted organogermanium compounds

Lutsenko, I. F.; Baukov, Yu. I.; Burlachenko, G. S.

doi:10.1016/s0022-328x(00)80204-1

Cited by 16 publications

(1 citation statement)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The procedure used for the preparation of allylgermanium trichlorides was an adaptation of the method reported by Lutsenko for the preparation of halogermyl acetates from the corresponding esters of tributylstannyl acetic acid [9]. The two reagents were combined in a 1:1 ratio without solvent in a sealed flask and stirred for several hours either at room temperature or ca.…”

Section: Resultsmentioning

confidence: 99%

New synthetic routes to allylic germatranes

Faller

Kultyshev

Parr

2004

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Section: Resultsmentioning

confidence: 99%

New synthetic routes to allylic germatranes

Faller

Kultyshev

Parr

2004

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Synthesis of Germatranyl Derivatives of Esters of Carboxylic Acids via Organometallic (Si, Ge, Sn) Reagents

et al. 1997

View full text Add to dashboard Cite

Trialkylstannyl esters of tris (2-hydroxyalkyl)amines, N(CH2CHROSnAlk,), (9-11) (R = H, Me; Alk = Et, Bu), react with X3GeC(R1)(RZ)COOR3 (12-17) (X = C1 or Br; R1, R' = H, Me, Ph, SiMe3, COOEt; R3 = Me, Et) to give esters of a-germatranylcarboxylic acids, N(CHzCHR0)3GeC(R1)(R2)-COOR3 (1-8), in high yields. The synthesis of esters 12-17 is reported. Esters of a-germatranyldiphenylacetic acid 24 and 25 can be obtained by treatment of diphenylketene with Et,SnOMe to give in situ Et3SnC(Ph,)COOMe (23), followed by reaction with GeC14 to give in situ Cl3GeC(Phz)COOMe (22) and further reactions with 9 or 11, respectively. Reduction of germatrane 6 with LiAlH, in diethyl ether leads to cleavage of the germanium-carbon bond with subsequent formation of (2-hydroxyethy1)trimethylsilane. The crystal structures of 3, 6, and 7 are reported. 1-Acyloxygermatranes 26 and 27 are obtained by treatment of l-methoxygermatrane (28) with diphenyl-and dichloroacetic acid, respectively.Interest continues in metallatranes N(CH2CHAlk)3M -Y (M = Si, Ge), having been reported some years ago for the first time; the main focus has been the nature of the transannular M-N bond [']. However, theoretical aspects of the research on metallatranes did not render synthetic approaches to a second-order problem. Moreover, many silatranes and germatranes show biological activity, which makes them interesting for medicinal chemistry and pharr n a c o I~g y~~-~] .So far, functionalizcd silatranes and germatrane~[~-"I, e.g. metallatranes with a functional group (e.g. C=O, C=C) in the p position to the metal atom, have not been studied in detail. Similar compounds belong to a more general class of a,x-conjugated systems, with characteristic features of the relatively labile metal-carbon bond and (e.g. in the case of p-0x0 derivatives) with the ability to undergo isomeric transformations under catalytic conditions or on heati11g[12-141. Whereas the synthesis and reactivity of 1-aIIylsi1-atranes were subject of numerous investigations, there is almost no information available on the chemistry of l-allylgerniatrane: only cleavage reactions of the Ge-C bond in 1 -allylgermatrane were reported" l]. Our investigations included reactions at the C=C bond of I-allylmetallatranes which occur with retention of the "atrane" skeleton and the metal-carbon bond, e.g. the cyclopropanation of l-allylmetallatranes (M = Si, Ge) [lo~'l].In this paper we rcport on the synthehis and properties of the series of esters of a-germatranylcarboxylic acids 1-8, starting from trihalogenogermanium dcrivatives 12-17, and tris(2-trialky1stannoxyalkyl)amines 9-11. Other organotin reagents, e.g. Et?SnOMe, were also used in the synthesis of I-acyloxygermatranes 26 and 27. In addition, the crystal structures of compounds 3, 6, and 7 are discussed in comparison.We have recently described the synthesis of the first of p0x0 derivatives of metallatranes: silatranylacetaldehyde and 3,7,1O-trimethylsilatranylacetaldehyde, N(CH2CHR0)3Si-CH2CH0 (R = H, Me) [6]. The compounds are air-stable and unde...

show abstract

Réactivité des trialcoylalcoxy‐ et dialcoylalcoxychlorogermanes et de leurs isologues soufrés vis à vis des aldéhydes et des cétones

Dousse¹,

Satgé²

1971

Recl. Trav. Chim. Pays‐Bas

View full text Add to dashboard Cite

Aldehydes and ketones add onto the germanium-oxygen bond of triethylmethoxy-and diethylmethoxy-chlorogermanes with formation of the corresponding germanium a etals, the stability, the mode of thermal decompositionThe germanium acetals of hexafluoroacetone are stable. &Elimination reactions are observed from germanium acetals of chloral and hexachloroacetone. The decomposition of the germanium acetals of the aldehydes and ketones takes place, in the presence of HzPtCla, to give the corresponding acetals of the starting carbonyl compounds and trialkylgermanium oxides.Additions and decompositions of the same type are observed in the action of the aliphatic aldehydes on the trialkyl(alky1thio)-and dialkyl(alky1thio)-chlorogermanes. Chloral gives a reversible insertion reaction, however, at 90". besides the ,!?-elimination reaction, a chlorine-methylthio exchange reaction is also observed with formation of tri(methy1thio)acetaldehyde and triethylgermanium chloride.The influence of the inductive effects of the substituents on the germanium or on the carbonyl group in the course of these reactions as well as the catalytic action of the chloroplatinic acid or of zinc chloride seem to confirm the addition mechanism considered. and certain properties o 2 which have been investigated.

show abstract

Functionally-substituted organogermanium compounds

Cited by 16 publications

References 5 publications

New synthetic routes to allylic germatranes

New synthetic routes to allylic germatranes

Synthesis of Germatranyl Derivatives of Esters of Carboxylic Acids via Organometallic (Si, Ge, Sn) Reagents

Réactivité des trialcoylalcoxy‐ et dialcoylalcoxychlorogermanes et de leurs isologues soufrés vis à vis des aldéhydes et des cétones

Contact Info

Product

Resources

About