CONFIDE 11TIAL Research Development Establishment,
British-Amrican Tobacco Co.Ltd.,
SOUITIAMPT011.
30 th August, 1957
VISIT Or DR. MRjr~ XPD 1.71. COMOR (Messrs.
Johnson, Matthey Ltd.)
28 th August, 1957
Present for D-A.T. 11. D. Anderson, Esq.
Dr. D. G. Felton
Dr. 1. 11. Hughes
Ile discussed in detail the aldition of 0.1 to
0.01%. of
pIntilium to civarettes in the form of a ir.-.ter
soluble compound,
the hope Le jil-, thr~L it vould have some effect
on the prorlut.-ts
arisin,g, from combur-tLon, elffier by.caLalytid-
oxidnbi.on or by
effecting a build-up of complex molecules from
free radicals.
It 1.,ar a,,,rced that the most oultable
C01-100LUld VLRA Platinum arVno-
nitrite/(1!113)2 Ft(IJO-))2. This compound Would
deconpose between
300-4000C to give elementary platinum, ammonia and
oy-ides of
11 itroccn. It would also be ear-ily solul,le to
the extent of I','
in water.
It i!as agrecd that we should use at a
concentration of
0.1~, measured as elcmentary platinum to weight of
tobacco (12,f.
moisture).. and that IlencrE!. Joluicon Itatthey
would provide us with
about 20 g. of the Mf-Po nitrite free of charge.
Ile would spray
cut rag irilth the solution, make into ciearettes
on a cigarette
irktking machinc and thnn smoke sufficient to
enable w to do analyses
for Bp., whole tar, nicotine, and neutral tars* In
order to
attempt to cIcterrine whcLher any elementary
platinum is carried
Un
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- 2 -
Styrene is still. a hIghly "acrtive ruboUnce, " by
further
reaction vIth atITIone (or butndiene) enn-prodir:9
a variety of polynuelear
condonsed etructures. Hoot of the conpouruls Vdch
have a ZErM
connection =y be deriTsd (theoretically at leant)
in this vay. Host
have boon isolated from cracked petroleum
fractiona.
b) Low-temnerature Carbonination - Coals consist
of regions of
ordered graphUla structure (domains) scattered in
a random fashion In
a matriz of dir-ordered aliphatic chotinr* On
coking or lov-tenTerature
carbonication, X-riq studies ruEgest tbat the
ordered dortains agglomerate
with the progressive disarren"nes of the rnndt-m
aliphatic rintrix.
Thin lons, which occurs in the region 700-700"~ Is
rreon- anted by the
conco-Atant fern.-itien of IILht hydrocarbon ells
and g,nes aml of
relatively larre anotaite of heaV 1-yMmarbon tarr,
i4vich contain a high
proportion of POPSTAL-like rubatnncep. The procers
by i-hich the
aliphatic untrix Lis converted Into the heavy
Wrocr-rbon frection has
not bocn studir-d here, ao yet, hit it Pe" very
pmrivible that the process
is clocelT ttnnlo~wts to that In (a).
c) _t'W1Yr1n of Tobneen r1xt me - Tobnceo-l-mf
eantains a
mi:-Tturv of long chain 1,armj finte bydrocarbma,
tbe hlk being hontac,)sane
(C27"56) and hentriacontane (C3111,64). Rocently a
lonj chain rolyens,
has also been lenlated from Pri.-,ht tobacco
Sopt.22 isrue).
This mixture of p?,raffing Me bnon rubjectoA to
pyralytio deernAutton
at BODO in the presence or nbconce of a mirface
catalyst (pwtes) both
in the presence and absence of air. (Lam , Act4%
ratholorica et
111,mbi6lo-lea, rcnmi1wmTIcm. JZ 421 (1956) ). Me
rroducts of pyrolysis
ware extracted nrA purified by chron-itogzw-17.
The rreaence of a
nunber of relatives of DORST&L and of P-'MILL
Itrolf ims inilicated by
ultra-viclet epee trophotometry of tho piwifled
fractionry. Lam curgeets
that tbe paraffins are drL7rdded tl,ernAjj~y to C~
frrg"onts, ~.e, en
ethyl a,
ncotyloro~ ultich then recombine an inclicated
above.
The evidence %hich has b"n culled fron the
literature no
notecl above all roints to the formation of
DDIISTAI-111ce oorpotmft being
due to an endot1wrnic erneYing ~-f lonn chain
paraffinic systeno to &-a11
un!:aturatod C2p C3 or C units, iiileh then
reconilive mmthernicnIly in
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varims ways to highly emplicated, stable
structures. It may be added
hors that the evidems at prevent suggests that
DOM-TAL-like compounds
are not readily recracked to an-11 fragments. They
owe their stability
to their high resonance ensrL7 which Is indicated
by the mavy ecguimaeut
Canonical structures which may be written.
Thus ac7 c~y-Jeq which nay yield ettqlsne~p
acetylene or
like structures, on pyrolysis, should be suspect
as possible sources of
DOPSTAL-like coupounds an ocabustion.
is
FM at present /compoeed of -
a) ISethyl cellulcre
b) Polyvir7l alcohol (nnc)
c) Hacamett7l--netetrwina (Hex)
d) Trietiqlans glycol (Trl;)
e) Tobacoo 11our
At prefert, po2ptlVlene glyc--lz ere also urxier
consideration
an possible replt%e--,-ntq fcr Tro as
pl&:!ticjMrg.
a) fiethyl coUla "s - tle haTs r-.-)t been able
t-7 firA any references
to the pyrolysis products of mtbvl cenulors,
Callulone itfsalfp at
high temerature, Undergoes drastin decor.Tosition
"with the proftction of
carbon dioxide, carbon monoxide, istar, ~
-glucozan and minor anounts of
bydrocarbons such as mathans and eftylem".
(cellulose aM CallaIMM
Derivativest rart 1, Edited by Ott and Spurlin,
Interacienow, W.I., 1954
p-179). Dr. TPj&as has reported socte unpublished
results from Birmj=tbam
University in,11cekting that benzene and diphorql
are formed to some artent
In T7rolyaln of callulors. There seens little
reaftan to ouppone that
replammt. of sone of the Lj&,-ql grcqns by
notbox7l radicals will.
affect thin brond generel.1sation, and since
naLural tobacco leaf contains
a(ris 10% or callujosic materials, the difference
would appoar to be alight,
C7)
Circe only 8.15% of the finlehad PCL in methjYI
cenulone.
b) rnlvviml Alcoh-I - The structure of PVAIe may
be written
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M--1 doo-%tLcn of this pol"ar occurs by randou
scission
.s. Further processes stdch mq be
of any of the (equivalent) car~c~bon linj-
Onvifftrsd are dehydration, by loss of the
elements of water, to yield
unsaturated fracments. The ultimate unit to which
the polymw mW be
reduced in athylenel but short chain uneatursted
hydrocarbons rq also
possiblo. Pr- MOverdon, at a= Ougges'.1on, has
carried out a tTief
--inati- of p7rolysis produfte of PVAlc. This
substance we heated
in a 6trOW of drY nitrogen and the gaseous and
volatile products driven
- into PGtW'dW Pft=ngMnnt9 solution or brorAna
Water. Both them
retagents were rapidly decoloriLred, the lattex
x.-Ith piwataneoijup dMosItIon
of an oLl, iMlcatinr- tho presence of unsaturated
substances of high
-IntlUtY- The OdOw Of P7rol7sing PVAlc to
chtractoristlenlly sweet-
taftifte?p reminiscent of that of ethylene.
It Onems likeY VInt OttqIPM nM other 2,)v mleculnr
-.-nigbt
unnat-ted t7droftrbone v411 be initial r-ducts cf
the Vturnal degradstion
of FVAIC.
15) F-ft-thVIOn~--mire - The structure of this
oulstance Is
- C-14"
N
,
rq' \ N
ICU,
It is a cMtalline, ertal2e cam-aund *Loh W be
v.3bilmd, but
which In acid solution liberates formaldebCyde,
There is no Inforlstim
---IM Its P7rd1YWi2 Products. However, since there
ar, no esibm-
Carbon 1* bonds in the molecule, there is no
reason to portulate the
fOrMatim of et?WIMO ate. an r7rolycle. In the
presence of sufficient
aqMp the carbon frapents vill fom cuton dimddo,
*119 in an
coquen-deficlent atmosphere b7er=ymrthyjwdDeg and
even vethnne ney be
Produced. It is conceivable that carbon-carbon
union way comw by a
free 2WILcal pro se, but there In no evidence to
rupport it.
It would spoear thtt Rex is Inn-c-cums.
d) Triethylenerlyr-1 WA 1nO1T6thT1WW PITrnIN - The
structuzW of
these comounds my be %ritten
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C14,
-I for TFG
CIA, 0-tv,
smq probab:Le that hwestoos pyWytlc reactions
A.pain, it Be
could remilt in tho formation of ethylene or
acetylene by dft,4ratUg
reactions, e.g.
c tA.L-. o - CKL C 14,0 H
-
under oxidizire., card-itions. Once nore, evidence
Ir inaking no to the
nmttwe of the proclucte ectu-02y f,~rrjed by
pyrolysis.
e) Tobacco Flo,.w - Un-Iew Intensive
Inveottg--tion, but excluded
fron this asvew.--nt k%r obviriv rensons.
Cono-1 Ufdo"
It caamot be too otrongly emphasived that the
conclusions
dra-m aboTe are IWely theoretical and are alwat
entirdly imoMported
by experimental %mk. F37olyt:ic studios are ncyt
thoce vith vhiah the
more acadenic chonirts have concerned thweelver.
Hoot Industrial studies
remain unpublirbod, If they have indeed been
vndertaken at all. Work an
thernal stability of polymers, both natural and
synthetic, or of other
orgmic compounds, e.g. plasticizers, is largely
concerned Ath
temperatures wall Ivlov thone ermountored in a
cigarette PM does not
reach deetraction point inch as to net with In
p7rdlyveo.
These reserrations seriously impair the val-ae of
the assesment
C7)
C::)
made. 149 have, ~wavcz, attemp'ted to Fclvv an
idea of the type of
----I
proqlucto to to expected.
This evaliuntlon %d11 te reviand in tho lipht of
nev findings.
BATCo document for Province of British Columbia 2
November 1999