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ST·rDIR9 ST·rDIR9 THE IN IN THE FIELD FIELD OF OF ORGANIC ORGANIC GERMANIUM GERMANIUM COMPOUNDSCOMPOUNDS V.P. V.P. MironovMironov andand institute institute of of chemistry chemistry State State scientific-research scientific-research Moscow, Moscow, compotndso, compotndso, USSRUSSR technology technology of of organoelement organoelement Our Our studies studies the in in the field field of of organic organic chemistry chemistry of of ger-gertwotwo (including (including in inmore more 200 issues issues presented presentedthen then 200 manium manium monographs) monographs) were were commenced commenced and and are still in in pro-proin in 1955 1955 are still green*green* The The comparative comparative of studies studies of chemical chemical oonversions oonversions ofof inin the the Group Groupelements elements lTD lTD analogous analogous compounds compounds within within single-type single-typemade made reactions reactionspossible possible it it to to conclude conclude that that inin the the chemistry chemistryGroupelements elements Si, Go, Sn, of of Group M-h M-h (Cy (Cy Go, Sn, Pb),jPb),j Si, after after obvious obvious substantial substantial change change between ohumioal between ohumioal proper-properties ties during during transition transition carbon from from carbon to to silicon silicon there there inin another, another, less less pronounced, pronounced, change change between between gemanium gemanium and and tin,tin, derivativesderivatives of of gezranium gezranium and and silicon silicon chemistry chemistry i.e. i.e. the the despite despite fact that the the fact that it it has has much much common common features features differsdiffers greatly greatly the from from chemistry chemistry organic the of of organic derivatives derivatives of of tintin and and lead*lead* Initially Initially the the chemistry chemistry of of trihalogezmanes trihalogezmanes (HGeHal(HGeHal 33)) received received primary emphasis. been been found that with primary emphasis. It It has has found that with con-conJugated Jugated dienes dienes the the reaction reaction proceeds proceeds as as follows:follows:

CC

+ +HGeHalHGeHal 33

[[ GG

GeHalGeHal HHal,HHal, 22+ +

ioe. ioe. was was for the first time time found that it it for the first found that trihalogeizmnestrihalogeizmne can can bea source source be a for for reactive reactive germanium germanium dihalogenides dihalogenides ofof oarbene-type:oarbene-type:

HGeA HGeA NGenal NGenal

GoeHalGoeHal+ +Hasa.Hasa. 22

With With others others or or amines amines in in reaction reactiongiving giving medium medium ethe-etherates rates or or aminates aminates with with HEoefal3 HEoefal3 the the above above equilibrium equilibrium movesmoves to to the the right rightthe the and and hydrogezmylation hydrogezmylation reaction reaction (I) (I) forfor ezmple, ezmple,the case In Inthe case of of allyl allyl chloride chloride Is Is displaced displaced byby hitherto hitherto unimown unimown condensation condensation double (II), (II), double germylationgermylation (IV) (IV) restions:restions: and and polymerisation polymerisation (111) (111)


·°1·°1
CECE OHOH Cl (I)(I) Hal3GOIHal3GOI 22 Cl 22 22 -ether HeHal3 HeHal3 -ether (11)(11) Hal 3GeCH3OHWCH2 3GeCH3OHWCH2 Hal CH2hCHCH2C1 CH2hCHCH2C1

(III)(III) Gea Gea GOOH Hal 33 Hal GOOH
withwith proceeds reaction reaction essentially essentially Hydrogermylation Hydrogermylation proceeds thethe It containing multiple multiple It opened opened say compounds compounds containingbonds* bonds* say ger-gerorganic organic oarbofunotional oarbofunotional obtain obtain to to possibilities possibilities broad broad re-reto to tendency tendency The The unknown. unknown. previously previously compounds compounds manium manium Cl Cl I. from from increases increasesto to I. TheseThese and and (II), (II), actions actions(III) (III) (IV) (IV) amine.amine. ether ether without withoutor or proceeds often often reactions reactions proceeds reac-reacto to capable capable organohalogenides organohalogenides other other and and Iodides Iodides con-coninto into actively actively enter enter to to SN1I SN1I mechanism mechanism tion tion according according reaction (II):(II): densation densation reaction
-RHal HGeHal HGeHal RHal 33 + +

RGeHalRGeHal 33

-; CH·CCHCH·CCH 22-;-; SiR3; SiR3; Ph3C-, Ad-; -CH-CH m RR m where wheret-Bu; t-Bu; Ph3C-, Ad-; 22 22 -; PhCHPhCH 00 00
-CH2OCH; -CH2OCH; Ph PhCNOR·- CNOR·- /NOR2/NOR2 Ph Ph

-; 2 2 3 3 Ph~CPh~C -; %-Is," %-Is," 22 22 can can also also en-entrihalogezranes trihalogezranes of of complexes complexes The The amine amine reaction.reaction. in in ter ter this this HSiClHSiCl?? and and of HGeCl3.R? HGeCl3.R? 33oR oR studies studies The The comparative comparative of preparati-preparatiand and opened new new their their close close similarity similarity opened revealed revealed hit-hitcompounds compounds silicon silicon and and the for for germanium germanium ve ve methods methods the non-availabe:non-availabe: herto herto S±'1.CHSA: S±'1.CHSA: C1CHC1CH 22
AI01IAI01I

-7%-7%

RI RN*1H1C1RN*1H1C1 RI 33

(.'0%(.'0% CEO2=CHCH2MCl, CEO2=CHCH2MCl,

RMOl3 RMOl3

(-50%)(-50%)

I Ia a and Si .. where whereGe Ge and Si (III) (III) pro-proreaction reaction double double original originalgezuylation gezuylation The The with somesome prooeeds prooeeds oonventionalit oonventionalitwith ved ved alsobe be also to to enough enough ocompounds:ocompounds: aoetylenio aoetylenio and and olefinLo olefinLo

,.I-


++ HGeHalHGeHal 33 -C -C C- C-

HH 33 GeC-GeHalGeC-GeHal

The The simple simple preparative preparative for methods methods for trihalogermanetrihalogermane etherates etherates and and aminates aminates obtainingas as obtaining as as well wellGeHalGeHal 2 2 dioxo-dioxonates nates from from available available hydrosilanes hydrosilaneshave have and and GeHalGeHal beenbeen 44 found:found:
,, Ether.Ether.

Rihier Rihier HGeHalHGeHal "2R"2R 33 22 GeHal GeHal EiR0Amns EiR0Amns HGeI~al HGeI~al OROR or or (l3Me(l3Me 22 0 Dioxag Dioxag GeHal Si)Si) 0 22 GeHal 22 Q~Q~ Dibromogermanium Dibromogermanium became be the dioxanate dioxanate to the mostmost became to be convenient convenient one one series series in in of of synthesis. synthesis. It It is is establishedestablished that thatreacts reactspractically practically it it with with any any organobromides:organobromides: RBrRBr _ _GeBrGeBr -e-- Br3GeR Br3GeR (-80%)(-80%) 2 2 -e-where whereAd-; Ad-; Ar-; 22 RR -Ar-; -CH-CH Br; 22)nC00Me; )nC00Me;22 Br; -(CH-(CH -OH-CH-OH-CH ;; -CH=CHPh; -CH=CHPh; -CH-CHBr -CH-CHBr etc.etc. Trialkoxygermane Trialkoxygermane aminates aminates (new (new complex complex germaniumgermanium compounds) compounds) have have substantially substantially the extended extended the synthetic synthetic pos-possibilities sibilities in inthe the chemistry chemistry of of germanium germaniumcom-comorganic organic pounds:pounds: N(CHN(CHOH) 33 CHCH (Eto) 3 GeH*R· ?. (Eto) ?. GeH*R· 22 22 OH) ~(0HH)~(0HH) 3 O_=__[; O_=__[; (0to)33GeCHGeCH000R.000R. (0to) 22 CHCH 22

In In the the casec. c. , -unsaturated -unsaturated case of of , carbonyl carbonyl compoundscompounds it it is is unnecessary unnecessary prepare to to prepare separately separately triohlorogermanestriohlorogerma end end their their etherates; etherates; it it is is sufficient sufficient to to mix mix three three star-starting ting reagents$reagents$
R' R'

20e20e
---

2 2eR'eR'

0H0H R+ GeHal 22 + 0 --22-CHOO-CHOO +GeHal 44 +(ra(ra BSi)BSi) 22 R 22 0

oGHoGH 22oooo 3 3 oHoH 22 RR 22

(-,o0%)(-,o0%) where wherea H, R R H, Alk, Alk, 0l; R'- Me; Me; HalCl, Cl, a 0l; R'- H, H, Hal -Br.Br.


restIs restIs into ineXpeoted ineXpeoted withwith enter enter into Trihalegeznanes Trihalegeznanes
oxide:oxide: ethylene ethylene and and aldehydes aldehydes keton6a, keton6a,
HIGCCHOH HIGCCHOH Cy Cy 0 0 HaC HaC PH PH 5 C1C1 13eHC13eHC 5 CICI GeCHGeCH 0H 0H __ __ HalHal GeCHGeCH GG ·· HalGeH2H2H HalGeH2H2H CAIICAII /HaL/HaL 33 22 33 22

SS
Me Me0 0
¶, ¶,

HaIGeHHaIGeH

Me Me MeMe

GeCCHGeCCH CMe CMe Ha1Ha1 22 33 MeMe

Hal3GCHOHGeHalHal3GCHOHGeHal

GeClGeCl for for 22:: can can be source source be a a Trichlorogermylmethanol Trichlorogermylmethanol + ClGeCHClGeCH 22OH OH+0 0 00 -GeClGeCl * 0 0 22 *

00

2I2I

of of elementaryelementary i.e. i.e. interaction interaction direct direct synthesis synthesis The The muchmuch have have been been attracted attracted silicon silicon with with organohalogenides organohalogenides of of ger-gerorganic organic compounds compounds The The first first attention. attention. unsaturated unsaturated ofof By By involving involving by by this method. method. have have prepared prepared this manium maniumbeen been the the diffe-diffein in synthesis synthesis and and -silanes -silanes ,,-halomethylgermanes ,,-halomethylgermanes on on basebase have have prepared; prepared; been cyclic compounds compounds been rent rent bridged bridged cyclic have have synthesized:synthesized: been them them gemaadamantanes gemaadamantanes been of of ClCl

CHCH 2 CICI 22

2

""2 ""2 OHOH 01Ge 01Ge ~ ~ Ge Ge l2 A l2 A ClGe ClGe 21 21 1Ge~l 1Ge~l -2-2 Ge1Ge1 CC OGe OGe 1 1 CH2 CH2
NGeClNGeCl 22

//

CH CH l l 22

CROCRO 22

--

germaoyoloalkanesgermaoyoloalka other other and and 1,3-Digeemacyclobutanes 1,3-Digeemacyclobutanes of of type:type:

ee

OHOH 2 2 ,,
VMS2VMS2

MeGe MeGe

S1 S1
i! i!

directdirect both both by by been synthesized synthesized i i a Sig Ge, have have been where wherea Sig Ge, synthesi..synthesi.. and and organometallia organometallia theirtheir in inoonth tt m The The briged ger ger m compound compound oonth to to briged
;; ~reaction· ~reaction·

the following following to to the more more showed showedtendency tendency analogues analogues silicon silicon


me3-GeRGeMe me3-GeRGeMe GeMeGeMe + G-Ge G-Ge RR 3, 3, -4 4+ NHNH where where 22 ; CC 44 ; 0; 0; R R = ; 22 ; = CHCH HH Germazanes Germazanes proved be are are proved to to more more be reactive reactive than than silaza-silazanes nes with with protonated protonated compounds:compounds: Me 33 Me GeNHGeMeGeNHGeMeHI HI 3 3+ + MeMe GeXH?H? GeX + + 33
carborane ** -XX where whereacetylene, acetylene, carborane

Pinally, Pinally, more new one one new reaction reaction Ge-C bond more for for bond formationformation Ge-C CuCu

has has been been found%found% GeHalGeHal+ RI 4 4 + RI --

RGeHal,RGeHal,

where R a Me, Me, CH21t CH21t where Ra )CS,n-PhI, n-PhI,All, All, )CS, Bu, Bu, o,-Naf,o,-Naf, m-Me~n-.m-Me~n-. Pr,, Pr,, Ph Ph

The The chemistry chemistry of of biological biological active active five-ooordinatedfive-ooordinated their ana-anagermanium germanium compounds (so-called germatranestheir compounds (so-called germatranes and and logues) logues) wellgermyladamantanes germyladamantanes as as well as as and and C-germylcarboxy-.C-germylcarboxylio lio and and hydroxamic hydroxamic acids acids received received the the particular particular attention.attention.
CH2 CH2 RR CH2CH2

00

.-.- e0-Ge e0-Ge

c 0c 0 II
RR RR R R

--

e'! e'! R00"R00"

oo
RR

II

Involving Involving germaniumin insynthesis synthesis germanium dioxide dioxide has has substan-substantially tially simplified simplified the the preparation preparation of of some some gezuatrmes gezuatrmes andand germaoynes, germaoynes, for for example:example:
00 "20"20C C

(..1oo,)(..1oo,)
OGe(0C1OGe(0C1 )?N1)?N12 22
2

GeOGeO CN2OH),3 3 CN2OH), 2 2 +N(CH+N(CH 22 H120H120

--

RN' EJ(CN"EJ(CN" 2 K& K& + Ge0Ge0+(110012)2 (110012)2 22 0WOH0WOH RN' 2 22

GeGe

Gezmanuji Gezmanuji dioxidealso also with dioxide react react with hemamethyldi·ila.u.e.hemamethyldi o· o· 1120 1120 (Ne3i)211 (Ne3i)211 00 ++ -..-.. o-G.(oS6i.3),o-G.(oS6i.3), 22
SS SS
--


The The extensive extensiveof of studies studies biological biologicalof of activity activity or-organio ganio germanium germanium compounds been compounds have have showed showedbecausebecause been that that of of low low toxicity toxicity they they exibit exibitbiological biologicalandand high high activity activity favourably favourably the affect affect the different different living living organisms. organisms. Besides,Besides, in incontrast contrast to to silicone silicone compounds germanium compounds compounds germanium compounds tur-turned nedto be to be less less toxic amongstructure-like structure-like toxic among the the oompounds.oompounds. Quite Quite possibly possibly germanium an germanium plays plays an independent independent role role asas a abiochemical biochemical trace trace element element its deficiency deficiency and and its couldcould doubtlessly doubtlessly itself inall all make make itself felt felt in living living organiuma organiuma asas well wellthat that among as as among organic organic germanium germanium compounds compounds will will bebe find find that onesgreat great valueuse use medical medical that ones of of value for for in in prepara-preparations. tions.

I

I

II

*14*14