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NOTES OF FREE RADICALS ORGANIC CHEMISTRY MSC 1ST SEMESTER.
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0% found this document useful (0 votes)
28 views17 pagesFree Radicals
NOTES OF FREE RADICALS ORGANIC CHEMISTRY MSC 1ST SEMESTER.
Uploaded by
Rãghåv PåñdëyCopyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
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/ 17
“OY
potcaL MECHAM
te ros ea hy be
o any
Ce te ep cele
ors en im kh dn
raat a ea in pe ee Poet
ee i em as
agen 0 -
{ere marca REACTIONS Ee “Poco tn fai a since
ment mre a net
ets set a a oto me tn sora
"Type af ree ri rt i Soe eee edge Se i ot oe et
cortices orb eaten | See in sien
whlch Bens et ie Th eee ean nnn nl nn el i i
‘i all pace me we exam Auoe
oo Soo
ors
Sern wot ct cin we ce
cer
so ras ah
gan econ TH eo me Se
oe in epg Se ns mal 2 gn Ham
nel ee ctly =CHt— Ch 9B ~~
vei #H—Be— FH, OO
ie as co igo ae
2 aston milo i
pengnge REE sian 5
arf rt rei 8 apni
Sra os beet Wea Rk
e act, —Etty —+ Oh) 10h =,
po tates sane +8 in tno eat. ne ty i ed
= eae tt mins ee Or
cep acne BaP same Pov en wn esis =
: : 20, 9 8-0-0"
bag ine may be eid sens tt sw donner i ie
i i ects moa
k k 7 rns feral etn:
minting Te cons nl carer ney ave ne ara
eco doen a {Rep cafe epee oe a
1 BRET tad o acne by pl fe ess a
pd
yey har a
4 Tk nis ae dered or he econ i
wer ROE
na enon se gai. :
me aly y= oe ee “
wa ven as se ed tal Stine 08:
vs vical is abstracted by note radial.
yt toe
(48) AICO ee
‘FREE RADICAL SUBSTITUTION MECHANISMS “|
Halogenaton a an Cin on ton Wi Oi ora,
tn ra Reem Sy,
“ Palees ae FCC
sino be applied alll hans conning may
can as be aplie at YF
‘exis
1 ec ot Tipp cme Sy
it i come fe Th eae
® ue oni a dBc pg
Beet con
st eran ern 0 ea a
te ene or eo Vole vaing pe of
an a eey ean paca
= pn oo allyl DON 3 fe ac en,
‘in
tough ie llowiag mest
Teision sep ee ™
Propagation ses RoWax” 9 ws
Wa; 9 ROX”
ext
Rae RR
“Termination sep
‘Toe ftlowing ste desesing oer feat halogens:
“The mont important single ator cag the ede of halogen recive en
cago HK bond wtih int de
W—FoH—C>H— Brom
“his etecse with ncressing HX bond ent che propane
RoHex 5 RS
is vod hich the te detening sep a et in theese of mee
‘iene desing oer the ene sbracto of lea i tp
sexiay Ht>secony He nay H > methane Ths orders easly eden
‘ane tas ofthe re aes ferme aftertaste of bydoae
‘Serwcemistty of Racial Sobattion * The ay ral hig pte}
ocd fom bh ces with gal neo form raceme mdf. Forex
(ly Chl, CH —CHy + Be? —+ CH, — CH, — CH,
es
we
‘eres ca be hss ne ap
inimide (NBS), Nchleonccngas aE Pig
(HBS), Noone gM ey
a
ale Bees
ners Ce at a
ca ten g
gy replete ote ls a ay .
# Neomioaing agen 3t poston to an nea OP a
=e Smt
a “se
eta ag
en cy — city St
9 Gy Hs Tag,” BT — met,
Cs on
Oo
jouemc— Hy BB+ Hem ec
cet Te coment
sent cel em ttt, ay
eo cares heaongem ne
yr me
Sip, — CH= +8" —s dy — CH ome
: ;
nen Bs 9 Gres
Sep 4 611; —cH—ctiy +815 —> Brat, cH ADVANCED Onaae
Foomatic lion ;
my
Org
= OCG
lech die Peete
ns canine cn,
eer rere
ae ;
L\, 2
erect iy a, — Ae 08 ay — on
,— = 8 tou
Free rac aon "
6%) Ch Bem — GI — BF Bs ay
Fee rata seatation
Br sym Cty pp CH=CH, EA Be— Ca, case
“Te akon of amie othe debi bond isles eerie oman hee
fon Lore era II te nocenaton of th rope bone-in se
‘8 Semetaes and ever 10 the ial spss andthe ale sabes en
‘cy Th cai nig cin wth ey ced
Incas whet alle itermedine is vse alc eerangenent een pt
i oto posite rds
eeu
cH, cm — cH
I
(, —CH— cmc, «city —CH= CHB
nn, | aoe emt =
ponte NE mag we se pnd has v0 dierent li poston, =
ee itaed moe rely thn span GE! ~Chaacy
nea sed BY th 3 ay I =O Oy
ra ole fo Bombe fh ies Ele aes HOH,
emit Sed Won eS a
nine im abana ce
ea ST peiamme tae ee
= Pa
oe act hy
on ciao ft
ni emt ae tc
se cn chee ee 99 a
sa tne ye?
acer erat BY he flowing chen in at nae
i
vue
Se shane
cH.
tomer
Gta,
Sel esa vet mice ye
see te mem mie emt ea
AP N=NK AN ax"
APL ae
Pec.one
sii tts a obtaoed fom thea rales peed fom ater 7
son of aay pero in oma sens ee
0 ° °
1 I
egal a AU NIH
Pam mea
‘shore et displacement mschitism was cdl tease
1 Karte maton of CC ond atte pene ty epee
carton oa ere pap nh eis ch eee
scsualy this is aot the ease. ite _ ee
2 es ot xin he fran of rfc Tan
ing wosty nec wich ser nh ein Se maa
pic ad wat propsd. Ts ur oe mena sa eee
‘motile substisations. saat oan
° ° ©
i i
NAC 0—0— Car 28h 0 240)
-0-[5-6-O-6
gat Meet ad is sailed by esac, Te min an i in
(8 sie couping eee
455
rates
ft tic Subst ; :
or Alle re ermines which produet will be formed ina
: va hs cio. A tee
rsp tat
a, ton steP fy a univalent (RydrOBeD OF halogen) and never a tena
1 ya a ae, For example, 3 Feacion between a chloe fe aio) ran
valet lea
Oe 03 fren:
sae CH3CH + HC OH =+3 kcal/mol
i
ag OE,
ClCH C4 All =#18hcanole
: valent atom is much more
a for this steric, A wi exposed to atack by
ai nan to Wit ghervaleney. Another reasons hatin eae
cece tt erty mor four
a ally ing isthe decreasing tdr of te ex of stain of
|Foeaeeo aant.
nds of ‘hydrogens
= veriary H> secondary H> primary H > methane H
sass coring 10 te rettive stabiies of the free radicals formed aftr the abstraction of
SE age of alkenes vinylic hydrogens a Tet abstracted, andthe abstaction of alle
nis eat prefee @ oer postions ‘of the molecule. This is because ofthe reson
“ion ofthe allylic radical =
ji aangements are common in these cases.
Ae ena sain of aromatic rings the preferential position of atack on Sie
nee aeenine ng, Aromatic hydrogens ae seldom abated i tere we ana:
ng
compounds containing electron withdrawing subtien, 68.7 Ct cH
rm 1 electron-withdrawing subsiens, 67 Olan)
{00H Coc, COOR, SO,Ct or CX) the Bpatlen age pedominny or excel it
fiat its Ts cae ec Si daring groups highly dezcivate adeeem
ns Conouns ike act cd and acy erie tracked at all. This is Becuse
‘tesons a lectopiic radials and look for positon of eh Sh density. Hydrogen: 00
SEB Nat the eleton- withdrawing groups have low = ens, therefore, the
steed at this poston, The aticls hate ot Jo te do nt sow BB
‘Spal oes not avoid the tack a he @ pos hile eas guy be
vag haetivity in 7a pence ai Tend to abstract electron-poor hydrogens a
oie re aremis Sutras ¢. Free rial bs Fran aromatic cain
kan ie hen i, Which a ring hydrogen is seed to give an aj aia: USA?
ilar that of aromat¢ electrophilic and nucleophile sso
Or — uo) $6 ———— 08:0
‘The following generalist
1 All substituents increase react
tems The em pele even econ donating Oey, |
ete Rene ada te news! seses and ae aM
frei he sate any signet exert heme ee
bodheectondonating and electon-withdawng groups sabia jh by
crm oa te I
CEP Where
5. Substiwents have a much smaller effect than in electrophilic or nue
6. Although hydroger
attack and ipso substation (3, with Br, NO. or CHsCO asthe leaving
found in certain cases.
Reactivity ata Bridgehead : “Many fe ratical reactions have been ober
carbons. For example, in th following reaction fre radical is formed athe badges
(or mectaism se Section 8.10)
This demonstrates that the fre radical need ot be planar. Although bridgehead fe ag
‘substitution is possible itis not preferred because ofthe strain involved,
Reactivity in the attacking radicals: “The greater the reactivity of a species, de aie
selectivity. The bromine atom is so selective that when only primary hydrogen are wea se
‘neopentane or rbutylbenzene, the reaction is slow or nonexistent. Isobutane x te akan,
brominated to give t-butyl bromide, and toluene reacts with bromine instantly, Other alice,
€g, ethylbenzene and cumene are brominated exclusively at the a positon emplaiay
selectivity of bromine free radical
Some radicals, ¢.g. triphenylmethyl, are so unreactive that they abstract hydrogens vey)
ls, €.g5 chloro, are electrophilic and some, eg. #8
‘nucleophilic. However, the predominant character of a free radical is neutral, whether it hs 2
‘As mentioned earlier, some free radi
electrophilic or nucleophilic tendency.
‘Th eet of saet on ratty: Unie fone sbsaons te ost
sin
those in the gas phase, where there is no solvent. However, in certain cases the sires
ppreciable difference. For example, chlorination of 2.3-dimethylbutane in aliphatic solver
effect on free radical substitutions, Free radical reactions in solution ae q\
com
oe
om, 0% (CH) ,CHCH(CHs}CH,Cl and 40% (CH),CHCCI(CHs ), wile a er
the ratio became 10 : 90. This is dae.
‘o complex formation between the aromatic
chlorine free radi
Heal which makes the chlorine less reactive and thus, more seleci¥®-
wie
a meta poston is almost equal t0 that of benzene, (°° icy 4
Para, on
=
“py
8 and
electron-donating groups. So ety
the leaving group in most free radical armen” cient
a
ety
COOAg Br =
By + am
fe
y
eS
ad
a 53 i —
—_—_———
peacTons “37
oarioN OF ALDEHYDES TO CARBOXYLIC AciDs
x vo earboayic acs as been carried out wit
ae ota ane R—CO—OH+ CHV)
jar with KMnO, also.
Tee ate, the snic mechanism is as follows :
Te alin peranente
8
9 4 1, Moe 2 28
Be, pec M2. RcoOH+ MnO —> RCOB + MoD, +
cn Bie n-th Are FO 006 + Ma +140
ou
sean at permangna, eon oi mice a een ose
° ono; °
I Is) 8 pene
pdm HM, —e RCH Ee ROG + MnO; + BH
bt) te ia
saul, wih x0, the one mechanism ss fllows
° oLton 9
B e
rdeneigo, <2 e-Gn | Be nope ned ran
evn le J,
eyes are also oxidised to carboxylic acids by atmospheric onygen. The drect oxidation
oat in his ease isthe peroxyacid RCO3HL which disproportionates with another molecule of
‘Wetyde to give two molecules of acid.
oO oO oO ° 9
I I l f to
RO HaR" 5 RHE RC —22> R-C—0-0° BH 9 RC H
i
aaa /RCHO $88 2009029 or
5.5] AUTOXIDATION—HYDROPEROXIDE AND PEROXIDE Fon, en,
‘ATIgy
“The slow oxidation (without combustion) of organic substances by atmosph, nN
a a ete hn cmp alors da
ce amas Tee eet
slime a ee oan *
ce othe i hretg a 2
exposure tothe atmosphere for along time. A useful application of autoxidation ting
acne os :
radical (Say Ris produced by some initiating step, itreacts with oxygen to give ig My
abstracts hydrogen. The folowing isthe eation chat ed
R10, 9 R00" Hy R'+R-0—0_y
R40; —> R-0—0' =" R—0—0— Ha Rue
Hyacpeone
[As with other free radical resctions, resonance stabilisation of teary (o 4 ee
secondary), benzyl, nd allylic earangemens ae common) fe radia he abe
these hydrogens is greatly facilitated, The following are actual examples rd
9-0-#
7 Me
On wine t..
1
Me Me
0-0-1
oo* dO c0*a
Another susceptible position is aldehydic C—H as already discussed above. The «pains
‘thers are also easily attacked by oxygen. This reaction is responsible for a hazard in he sere
‘ethers because solutions of these hydroperoxides and their rearrangement products ia eh =
potential spontaneous explosives.
1 |
sel ans — Fn Gr0- OB
Hydroperoxides decompose further to generate radicals which start new chain reacts
R—O—O0—H —> R—0'+0—H
R—O'+R-H —5 R—On+R
ion f 5,
‘The autoxidation of organic compounds is i er
Es pounds is usually inhibited by the addon Or
‘These compounds, which are usually phenols 2COr stroy the ch
es comp ly phenols or secondary amines, destroy
ROO" +HA —> ROOH+A* (HA =an antioxidant) yr OO?)
ros 40
9 exance sie ad eaves vrei
8 tance tn
en ;
on 00" +A’—» ROA
om AAA
is not capable of
oF witha similar
| at
ides
jon of PSI ay OOH —SE> ROOK
Y ie produced nto organic compounds by usiment wit
cane lord oor ells fs coal nd gue a
. vy goons
S| ema Ee presence
: ernie! caine The type of hydrogen replaced is mainly benzylic, allylic, and
fer HEE paism involved 8
oom ‘oon 22+ #00"
p—H+R00° —> R'+ROOH
: R’+ R00" —> ROOR
a FORMATION OF CYCLIC ETHERS
POA
coycHCH.CHOH pape
inbenene i.
“Teahydrofurn (THE)
ee ee ee es
seein high yes. Litle ono four and six-membered clic ethers nse and
si reentvey re obane inthe cave of alas having yor = hydoge, The
aneerTy ten card ot with a mixture of halogen (Bry or) anda salt or oxide of silver or
‘rauy (especially HgO or AOAC).
proposed for the cyclisation with lead tetraacetate, The step
'| te foliowing mechanism has been
| csi Aisa 15 intemal hydrogen abstraction which is greatly favoured over 1,4 or 1,6 abstractions.
& ty, BOM. CH, CH, A
ee ee
oH OPb(OAC)3, A _ o On
Bo(OAC)s Pore)
Qrnorrenon — fe Yn — ude
ae
PO{OAc)3
= $80 $$ 00 rn
COUPLING OF ALKYNES R-C=C—C=C_R
[8.9] ARYLATION OF AROMATIC COMPOUNDS BY DIAZONIUM salts |"
oo by
AVHtARNDX My Arar
‘When diaconuc salt solution is mae allline, the aryl portion ofthe diac ina
couple with another aromatic ring. Ths reaction is known asthe Gonberg or GonderBexc,
‘eaton, and has boon performed on several types of aromatic rings and on quinone Mio
GGomberg-Bachmann reaction i performed inramoleculrl. either bythe alain souawrhe |<
‘copper ion procedure, itis called Pschorr ring closure. ’
ORORIOMO)
(= CH=CH, CHCH,, NH, C=0, CHS]
‘Mechanism of Gomberg or Gomberg-Bachmann reaction :
eo ¢
ArN,X Ay ar
N—0nMNSNS gy No N—0—N=N-#
iho Aabyétide
N—Ar — Ar’ 40" —N=N—AP
o a
each the substrate to give the intra 0
Biv the product. It has been shovn that whatever is Seg
‘omtho or para substation always predominates, but ™
Ar—N=N—0—
‘The aryl radical thus formed at
radical I abstracts hydrogen to
substituent (R) in the substrate,
‘meta product is also formed, 461
4 penc5
ical
HAT 6 —NeNmar
o
O ek 4. + HO-N=N—Ar
+ wo
e f yction
yer rea ee
Cae AN, X —O% > rx +N [x =Clor By]
anna hcp clodecr bie aces er bois,
ae mn is called the Sandmeyer reaction. ‘The reaction can also be carried out with
sg case iti clled te Gatermann reaction. Toe Sandmeyer reaction
orton of fries and odes, but itis probably the best way of inroducing
he cles (Wo Steps The is step isthe eduction of iazon
ei aves Wo Steps Te fist step isthe eduction of iazoniu fon
ey acl:
os :
‘AgNaX +CuX —> Ar’ +Np +CuXy
sade wud sep th al ada abst aogs fom ep erie, ecg it cux is
7 catalyst.
etna a1
Ar’ +CuX, —> Ar—X+Cux
HUNSDIECKER REACTION
RCOOAg + Bry, —> R—Br+CO) +AgBr
teasion of «silver salt ofa carboxylic acid with bromine leading to an alkyl or ary! halide is
cane Hunsdiecker reaction. It is a way of degrading a carbon chain by one unit. Although
te the most often used hatogen, chlorine and iodine have also been used.
Vien odin is used, the ratio between the reactants is very important because it determines the
pdx. A: [ratio of salt to iodine gives the alkyl or aryl halide as above. A 2 : 1 ratio gives the
‘rRCOOR. and this is called the Simonini reaction.
‘Defollowing isthe mechanism of the Hunsdiecker reaction :
0
i
Sep L RCOOAS +X, —> R—C—O—X +Aex
°
separ —t
SrbRC—0—X —> RCO" +x" Gaitation step)
#9 3.RC00" 5 R*+.CO, G and 4 propagation steps)
SeP4.R'+RCOOX —+ R—X+RCOO’, ete.
cI
q 'HLOROSULPHONATION (REED REACTION)
RH4+50, +1 "+ RS03C1 OUNCE CROW Oa
cn ey mr iy ty meh Ae nd in
on OnwOA), Ho g
FAC Puong,
|
of \, L\
C Nermonen+ acon — Yn, fy
q 011 (AcoyP> on
Faorer,
acme 8, p_comc—cme—
ROH rg! AC
“Terloa alkynes can be couple by beating wih stihiomevic mounts of cupric sls in pyre
(x similar bake. Ths reaction produces symmetrical dynes in high yields and is clled Eglinton Reeon
Another common proceiure Is the use of eaalytie amount of cuprous salt in the presence of semen
x ammonium chloride, Amospheric oxygen o ome oe oxiking agen. permanganat or yoy
required inthis method, which i eled Glaser rection. Unsymetia dines ean be pepe by
Cutior-Chodkiewiez coupling (mechanism is not fll uadesent) +
R—CmC—H + —CmC—Br 5 RCC’ + HB
‘The mechanism of Eginion and Glsee reaction i outlined below +
Rome Ay om SF tome
2R-CmC > R—-CemnC—Comc—R
[183] anviarion oF AROMATIC COMPOUNDS BY DIAZONIUM SALTS
arts ask Bate
Wen onium lt slo is me tain ew orion of thsi sa can ol
wit ana soma iis acon omen a he Gonder Coc a en
on pfme on see ps of ata aps son ene Wie oe ean,
‘econ pafmed inranolcar er by he sae saon a ye pce ea
‘Fae Por rg care
GO- ero
= CH=CH, CHA, MK C=O. Cn) an
ay ou
pie 2 Anew
ArN=N-O-N.
an tis thus formed stacks the abtat to give the intrest fom which he eel
gone gen 1 Ive he poi. hes fen shown tht wheres he te fbn
- BD + HON=N—Ar
®
nie abst, ortho or pra subtiton always pedomintes, bt sl amount of meta products
Es
Amt SS acer
(X=Cl or Be]
‘retment of diazonivm salts with cuprovs chloride or bromide gives aryl chlorides or bromides,
seve, The reaction is elle the Sondmeyer reaclon. The reaction can aso be cried out with
red HBr or HC, inthis case it elled the Gattermann reaction. The Sandner reaction is 101
rr rte preparation of fluorides and iodides, but itis prabably te best way of introducing bo
{volves two steps The frst sep isthe reduction of diazonium fon by
conf give an aryl aca:
AWNaX 4 Cux —> Ar + Na+ CuX2
Inte second step. the aryl radial abstracts halogen from cup chloride, reducing Ht. CuX is
sented and is thus, a true catalyst
"AG +CaXp > Ar—X+ C0
[) WunsDIECKER REACTION)
coongs By — R—B19CO1+ ABE
Rescton ofa silver salt ofa carboxyl acid with bromine leading vo an aky! or an halide is called
‘Se Hnatcckerretion, It is way of degrading a carbon chain by one unit Although bromine is the
"at often used halogen, chlorine and iodine hhave also been used. ;
The ia cee cie ratio between the reactants is very important because it determines the
Fr AT naga oct to iodine gives the alkyl of 271 halide as shove, A: | ratio gives te ester
‘and this is called the Simonini reaction.
‘The following is the mechanism of the ‘Hanae yocion
Sup, scons +p R—C—O-K+ Aa
i
5p 2, pon ROOO' (eiton 909) ADIAICED RCH ou |
a 0 I HOO no i
at psn :
[Eat] ctorosurpHonarion (AED REAG 150%¢! 2
114802 Caine and sulphur dioxide is eaty
compan ilar to the halogenatign oe
Tre chorsphontn of xe ca sit
reaction. in scope an ange of prot bred
Carton discussed eer The mechanism ial sil
as
oy
pcnect— FHel
As
8-80} +Chh —? SOIC + Cl
chy —ci=cH—Cr,
' i :
sbu-cec + chy CHC chit
ee ieee yee |
theo rs aan met 3 ne iran of eb ig
armen ean ali iter cp wots a ee,
ee
ee agg
Bipnptkbayt| omega cane eran
ale Cr i oe eee geen ine wy
roe 9 CB)
I Inston I I
meme Ae fod oe ahd ty, Beene
t = (
Hy an chy
o
o
ey an) cH
Hammett ot Lan
Hy CHy
ay -
ts ch oo
Wel 9 Pi-f—0th + htc, eel
OVGAL REACTIONS ae
‘re yield of the rearranged product Il inereases with the dution of the reaction minture, This
tthe above mechanism because a decrease in the concentration of a hydrogen donor 1 would
sie orangrsent atte expense of the hype asraton by the ra 1. Pate. he rae of
‘eeaangenent i inhibited by the aon af a effective yngen donor suc a opel The
proceeds through the intermediate bridged rae
oe
jh ec kh
1 ay
cy ue
Hy
“The intermedia of a bridged radical also explins why a methyl migration doesnot take place 2s
rely abn cabocation eeangerent, Fora methyl migration va a ridge aia there wil be tee
‘ecrons sped over thre carbons.
Hy
abt,
a
fs
Molecular orbital eaeuatons have shown that such ridged system is very unstable as compared
toa two electon bridged system ofa carbocation
and dispopoionaton products ofeach of the following radials
) cH,eHcHy
1 Pritt con
(2) CHyCH;CH,CH
Fre radical chlcnation ofan alane CH ves nly one monochar dt
ihe abiae, (CHa,
4. Amange the following ompounds i
NBS NCS (Nechlresuccnimidey) Ch Fa
a > 8 > cS D
ofall he fee radical monocloriaio products of | 2-eoropropane and indicate
rivave. Wt he stature of
in oder of decreasing sletviy in ee radelhalogeaton =
4, Give the stetures
them a cial or achiral
‘Wite the products of brominion of |-utere wih NBS and ind the mj prod
{6 Predict the produ) inthe following reactions:
i co ste, CO o mrcnycrycr, + PHeHWCHCH
oH OF
“O23 3 “CC oa
i cy
0p © (00 Abnormal Rlr-Tlemann reaction
I Reenter noma ond sharma
Qn EN —- BRO
+ ho
Asoral acon Rg expansion) —
aa
Qa Ge
(Certain phenolic compounds aso exhibit norma and abnormal RR
non astonish ta ps
SANDMEYER REACTION
‘ts hades are mre ote reared om te ceesponcing accel by reacting te alshls wih PC,
‘SoCirerconcenated HVZnCl, Tha 2 Raes camo b prepare fom phar by hese maha. Ost
‘stogenaton of roma compoonds yl mitre of omer: fom whichis eit lal fhe Gees
‘Sendmeyer acon al 9 seh mated fr iad a halogen subettent ttho desind
pion ol narra ‘ia mena imeias we comaro an moms pinay amin so 69298 azo ey
‘reste i iow 2 na etree of mss (ly lo W380) ow oe
© 50) Stren one ameyergW cn hrS
‘San emcnamen ctbeante ee te van b topo a
Suse 64s
Mechaion
"seas actus copper hase pour wes dzeian en an sy ondaon-redon
|nvng escorts The copes across han stn ar
“To fomason of anal istrtaed ye ceconostion ef beans dazonium cide abe
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