Synthesis and Properties of Diorganomagnesium Compounds

189 Pages·2016·10.99 MB·English

by  Conrad William Kamienski

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Doctoral Dissertations Graduate School
12-1967
SSyynntthheessiiss aanndd PPrrooppeerrttiieess ooff DDiioorrggaannoommaaggnneessiiuumm CCoommppoouunnddss
Conrad William Kamienski
University of Tennessee - Knoxville
Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss
Part of the Chemistry Commons
RReeccoommmmeennddeedd CCiittaattiioonn
Kamienski, Conrad William, "Synthesis and Properties of Diorganomagnesium Compounds. " PhD diss.,
University of Tennessee, 1967.
https://trace.tennessee.edu/utk_graddiss/3077
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To the Graduate Council:
I am submitting herewith a dissertation written by Conrad William Kamienski entitled "Synthesis
and Properties of Diorganomagnesium Compounds." I have examined the final electronic copy
of this dissertation for form and content and recommend that it be accepted in partial
fulfillment of the requirements for the degree of Doctor of Philosophy, with a major in Chemistry.
Jerome F. Eastham, Major Professor
We have read this dissertation and recommend its acceptance:
Bruce M. Anderson, George K. Schwitzer, David A. Shirley
Accepted for the Council:
Carolyn R. Hodges
Vice Provost and Dean of the Graduate School
(Original signatures are on file with official student records.)
Novmeber2 7,1 967
Tot heG raduea Ctonucil:
I am subtmtiign heretwhia disesrttiaonw rtitne byC onrad
Wilimi Kaameinksie nittled "Syhnetissa ndP rpoertieso fD ioarngo­
mangeisumC omposu"n. dI recommentdh aitt b ea cecpteidn p atrila
fulifllmento ft her equimreetnsf or tdhereg eeo fD octoorf
Philoopsh,yw itah m aojri nC hesmitry.
Weh avre eadt hisd isrsteaiton
andr ecommeintd sa cecptance:
Acceptefdo rt heC onucil:
VicPer esidfeonrt
Grdautae uSdites and Reesarch
SYTHNESIASN DP RPOERTIOEFSD IORGANOMASGUMIN ECOMPOUNDS
A Dissertation
Presenttoe d
theG radtueaC ouniclo f
TheU nviersyi otfT ensnesee
InP atriaFlu flimlelnt
of tRheeq umiernetfso r tDehgree e
Doctor ofl osPohphiy
by
ConrWaidl ilamK ameinski
Deecmebr1 967
Tom y deawri f,eD iane
769836
ACKNOWLEDGEMENT
Thea uthwoirs hest oa cknolwegdet hek indnsesa ndg enesrityo,
asw ella st heg uidcae,n shownh imb yP roefasoJ.r F .E atshma during
hiss utdieastt heU nviesriyt ofT enenssee andd urnigt hep repairoant
oft hitshe si.s
Mayn thaknsa rea lsdou et o hetL ithimu Corpaotrino oAmfe rcia
andt ot hek indens,su nedrtsandianngdf orseihgto f iptrsse iden,tM r.
HarrDy. F etlentseians w ella s thheel opf m anoy theorfi tsem plyoee,s
withowuhtso es upporta cthhviieesm ecntou ldn ot hbaeveepn os sbile.
Grattiudies a lsdou et ot hea uthso rf'atheMrr,.W atler
Warchwsakl,ioa ndt oo themreb merosf h isf ami,l fyort hew onedrful
guidaanncdeu ndseatrndinsghw onh im throughhoiusct ar eer.
A specialn otoef t hanmkuss t ablesg oiv e�t oP roefssorM .z .
vonK rzywlocobkio fM ichigSaatnt eU nievrsiyt,w hosek indnsesa nda dvice
inspiretdh ea uthtoorp urstuhei csou rseo fs utd.y
iii
TABLOEFC ONTENTS
CHAPTER PAGE
I.I NRTODCUTIN O 1
• • • • • • • • • • • • • • . • • • • • • •
A.M ethoodfPs r erpaaitono fD iakyllmagnieusmC ompounds 1
• •
B.P ropertsi eoUfns ovlatde DiakyllamgnieusmC ompounds 8
C.S ovlatni aondt heP roeprtieosfD iaklylamgnieusm
Comopund.s . .. . . . . . . . . 12
. . . . . .
D.R elatCihveecm aiRle acvtiiyt ofM agensiumA lkyalnsd
GrignRaeradng tes 18
• • • • • • • • • • • • • •
E.M eatlaltioann dP oylmeirzaiotnb yM agnieusmA lkyls 26
II. RESULTANSD DISCIUOSNS 30
• • • • • • • • • • • •
A. Preparna otfDi ioaklylmnaegisumR eangtes 30
.• •
1.P reparaotfRi 2Mognb yM eatl-tMaelEx cnhgae
bewteeRLni and RMgClo rM gC2l • • • • • 30
2.D irePcrtpe raatni oof2 MRgf roMmag neisum
Metaland Alkly Cholrides 40
• • • • • • • .
B. PhysailPc roeprtioefsD iaklylmganeisumR eangtes 44
C.C omlpexeosfD iakyllamgnieusmR eagewnitths
BridgehDeiaamidn es 57
• • .• • • • • •
D. Metallaitonwsi tDhi aklylmagneismu Reagtesn 60
E.R eactnisoo fD iaklylmeasigunmR eagnetwsi th
Bnezopnhoene 78
• • • • • • •
F.M isecllaneRoeaucsto nisw itDhi aklylmangeisumR eagent8s5
•
iv
. ....
v
CHATPER PAGE
II. (CNTOINUED)
1. AttmpetedAd diitono fD iaylmlkagsnumie
ReagetnotE sht yleen • • • • • • •• .. . • • • • • 85
2. AttmpetedR eatcino ofd i--,!.Bultmyaegsnumi
Reagewnithts P heynldimelthchlyoorsliane
inE htyl Ethe• r• ,• • • • • • • ·• • . . .. . 85
3.E ffecotf D iayllmkangesiumR eagnetso nt he
Haolgen-MIenttaelor ncvresionR eactionw ith
AlkyllthiiumR eaegnts. . . . . . .. . . . . . 86
G. Homologiziaot'no Afl ykllihtimu Reaegnts• • • • • • • 81
1. Two OrdairnyR uns . . . .. . . . .. . . . . . . ' 88
2.F ouTMErD A-CatalRyuznesd . . . . .. . . . 95
3.S -Buytllihtimu uRn • . . . .. . . . .. • i . . . 100
4. Summary . . . . . . . . . . 103
:II.I EXEPRIMENTA•L• • . . . .. . . . . . 107
A .. IntroduIcntfoorarmyt io.n • . . .. • . . . . . . • . 107
1. Reage.n •t .s . . . . . . .. . • • • . . . . • • 107
2. Intsurmentaitona ndA naltycialT ehcniuqes • . . . '108
B.P rerpaatioofnD ilakyl�egsunimR eagefnrtoms
Gringaradn dO rgalnitohiumR eangtes. . . • • . 110
1. Preptaoirnao fD i-S-lbmaugtnsyeumi . • • . . . . • 110
2. Prepairoanot f Meltihbsyuotmayglnseumi . • • • • 111
3.P repairoanot fM etlh,!-y-butylnmaeigsum • . • . .. . 112
4. Preaprationo fS -Butlyhpenlymagsnumie .·• • • • • • 112
vi
·CHAPTER ·PAGE
III.( CNOTINUED)
5.P reparaotfDi ioinsb ouytlmasgumni e . 131
• . . .
6.P reparaotfDi oi-�n- ubtyalgmnseumi from
SmuiltanePourse paraot.fino-nB utiytlhlium
-
and-�-Baugtnsyeumil mChloride .. . .141
. . . . .
C.P rpeariaont ofD ilakylmasgumin Reeangtesf rom
Orgainhotlumi ReageanntdAs n hdyrouMsa gsnumie
Chlorei d . . .. . . . .141
• • • • . . . . . . . . .
I
1.P repaatrin oofD i-�-buatgynlemsium . . .. 141
. .
a. Fromd imetehhytelr -lsvoatbeydp- roduct
MgC21 . . .. .. . .. .. . . . . . . . . . 141
b. Frome hter-sdloevtaed�y -proudctM g1C2 . .. 151
c.F rome hterd-eslovateMdg1C 2 by-purcotd
fromr eaticono fa Gringarrde agent
witchhl orien . . . . . . . 161
. . . . • . . .
d.F rodmmi ethyelt herl-vastoecdmmo ercial
anhdyrouMsg C2l . . . . . . . . . . . • 117
e.F rome thyle ther-atcivadt,de eoslavted
commrecila anyhdroMugsC2 l 181
. • • • • . . . .
f.F rmo unsoaltvebdy p-roudctM gC12 181
• . • • • , •
g.F roumns lovatebdal l-meidll ulmcpom mericla
anhydroMguCs.2 l 119
• • • • • • • • • • • .•• •
h.F roma lco-hacoltviatde,d eslovatceomdme rical
anhdyrouMsgC 12 • • . • • • • • .• • • • • • • 120
i.F romd eoslvtaed mmecroicalM gC2"l62H0 • • • • 121
j. Frmo commericalp owrdeeda nhdyrouMsg C2l 12.2.
• . .
vii
CHAPTER PAGE.
II.I (CONTINUED)
·
2. Prepaireanet fEl iS--butlymagnseium 122
• • •. • • • • •
a. Frmo dimetlh eyther-solvbayt-epdudrc ot
. .. . . . ... .. . . . . '1 22
. .. •· • •
b. Frome there-sodlavteMgCd1 2 by�produfcrto m
reatcoin of iag naGrrreda gewnitth b enzyl
chlori.d. e .. . . .. . ... . . . . 123
3. Prpearatioof.n Di ,!-!bu-tylmagensium.. . .. 124'
4. Prepairoanot f. �ineopmaegnnteysli um ... 125
•
D.D irePcrte pairoanot fD ialmakgynlseuim.R eagents
FromM agnseium Metala ndA lkyClh lroides ... . . . . 1 26·
•
1. Preparaotfi· o:Din,!-- butylmagnesium .. .1 .26
• • • •
a. Ind miethyelt heyrc-lchoexanseol uiton 126
• •
.
b. Byv acu-umstripngp oifs olvefnrto tmh e
GrignarTeda ge,n ftollwoedb yr e-suotlion
inb enzene . .. .. .. ... 1.27
•• • • • •.• •
c. Ind ietheytlh er-bneesn ozleiuotn . ... . . 127
.•
2. PreparaotfiDi o-n,!� !.lntlymagnseumi • • • • • • • 1•2 8
3. Prepairoanot fDi •,!!•8Dylnmeasgumi 129
• • • • •• e-1• .J ..
4. Preparaotfi»i oinso pryolpmagsnumie . . . 130
• • • • e1 • ••
E.P repaTaotfiM oinex dS oulblDei ,n--�tlymaanieums.
Complexweist ,!h· Bultlyihituma n.da -Butlytlih ium 131
'
1. Preparatoifo n' »1-,!l!•·anebuatiyum 131
• • • •
2. PreparaotfiB ounyt llthiium-Blumatanyesimu
Complexe..s . . .. .. . . . . .. .. .. 132