Dorphine compound synthesis from pyrrole- benzaldehyde mixture by electrical discharg

Radzilowski, H.

Szutka, A.

English

NASA Technical Reports Server

and two percent xylene i n  benzene as  adsorbent and developing I 
r \ e  mixture respect ively.  2 1 Visible  spectra  of the zinc-chelate 
of the compound ccnpared wi th  t he  chelate  of the reference 
TFP. The yie lds  of the  compcund i n  the presence of  molecular 
oxygen, are increased over the  y ie lds  obtained i n  runs per- 
I 
CFSTl PRICE(S) s 
POEP3IWES-LIKE SUBSTANCES: 111. 
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SYNTdESfS BY ELECTRICAL CISCHARGE 
INSTITJTE OF SPACE EI3PEYSICS, 
UNIVERSITY OF DETaOIT 
DETROIT, FIICH. 48221 ff 653 July 65 
E l e c t r i c a l  discnarge between ar; elzztrcc?e cnmected t o  a 
poss ib le  under pr imit ive earth conditions.  
supported i n  p a r t  by Grant NsC-226-62 from the  National 
This work w a s  
Aeronautics and Space Adninistration. 
https://ntrs.nasa.gov/search.jsp?R=19660024084 2020-03-16T21:00:13+00:00Z
L 
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s 
AI'JTON SZUTKA AND ROIJALD H. 2ADZILOWSICI 
SYNTHESIS BY ZLECTRICilL DISCEARGE 
I n t r o d u c t i o n  
The appearance of t h e  f i r s t  l i v i n g  c e l l  on t h e  e a r t h  w a s  ' preceded by chemical evoluik-, L.es,  e v o l u t i o n  on t h e  molecular  
l e v e l .  It h a s  been agreed by s c i e n t i s t s  that t h e  e a r l y  Earth's 
atmosphere,  c o n s i s t i n g  of  methane, amxonia, water  and hydrogen 
under cons t an t  a c t i o n  o f  u l t r a v i o l e t ,  v i s i b l e  and nuc lea r  
r a d i a t i o n s  and e l e c t r i c a l  d i scha rges  wa6 c o n s t a n t l y  changing 
due t o  t h e  formation of more comslicated molecules. (1 v 2 9 3 9 43 
This atmosphere, r e d u c t i v e  i n  i ts  c h a r a c t e r ,  a t  some t i m e  
s tar ted t o  change i n t o  a n  ox ida t ive  one, due t o  t h e  appearance 
of  molecular  oltygen which w a s  be ing  forme6 bj. p h o t o l y s i s  and 
r a d i o l y s i s  of water vapor. Through the  a c t i o n  o f  u l t r a v i o l e t  
r a d i a t i o n  and e l e c t r i c a l  d i scha rges  on t h e  molecular oxygen 
ozone w a s  formed, which sh ie lded  t h e  E a r t h ' s  s u r f a c e  from t h e  
short u l t r a v i o l e t  r a d i a t i a n .  A t  t h e  s a e  t ime,  t h e  p h o t o l y s i s  
and r a d i o l y s i s  of water  &oduced l a r g e  q u a n t i t i e s  of hydrogen 
peroxide ,  which i n  c o n t a c t  with organic compounds would des t roy  
them, Therefore  a n  evo lu t iona ry  p r e s s u r e  w a s  e x e r t e d  on t h e  
system to :  
1) u t i l i z e  t h e  v i s i b l e  r a d i a t i o n  i n s t e a d  of u l t r a v i o l e t  
f o r  f u t h e r  chemical r e a c t i o n s  and 
2) d e s t r o y  t h e  accumulated hydrogen peroxide.  
1 
. *  e --- - . 
-2- 
- 
It has  been shown by Calv in  (5y6) t h a t  p o q h i n e s  o r  b e t t e r  
porphines  with a p r o t e i n  moiety, known as catalase, a r e  very  
e f f e c t i v e  c a t a l y s t s  f o r  t h e  d e s t r u c t i o n  o f  hydrogen peroxide.  
A t  t h e  same time porphines  beg in  h ighly  co lored  subs tance  
are caGable o f  absorb ing  v i s i b l e  l i g h t  and u t i l i z i n g  this 
energy for c e r t a i n  chemical r eac t ions .  It i s  known t h a t  wi th  
t h e  a i d  o f  porphyr ins  and e s p e c i a l l y  t h a i r  me ta l  c h e l a t e s ,  
chemical t r ans fo rma t ions  such as hyd,-ogen t r a n s f e r  or ox ida t ions  
could occur. 
. 
Thus t h e  ab iogenic  formation o f  porphines  and porphine- 
l i k e  subs t ances  is f o r  exob io log i s t s  or t h o s e  i n t e r e e t e d  i n  
t h e  format ion  of l i v i n g  s y s t e m ,  of outmost im2ortance. 
( 7 , 8 , 9  that It has  been shown i n  our p rcv ious  papers  
porphine- l ike  subs t ances ,  s2ecifically 5 , 3  , y  , g -tetraphenyl- 
porphines ,  can  be formed abiogenica l ly .  These pape r s  also 
p r e s e n t  t h e  e f f e c t s  o f  Co-60 gamma-radiction and u l t r a v i o l e t  
and v i s i b l e  r a d i a t i o n s  on t h e  r a t e  of formation. 
tetraphenyl-porphines:hae b j e n  s e l e c t e d  as a model f o r  t h i s  
t y p e  of compound s t r u c t u r e .  
The a,3,y,d - 
“his paper  p r e s e n t s  another  obse rva t ion  having d i r e c t  
b e a r i n g  on t h e  format ion  of t h e  organic  m i l l i e u ,  namely t h e  
s y n t h e s i s  of porphines  from simple p r e c u r s o r s  and t h e  e f f e c t  
of e l e c t r i c a l  d i scha rges  and r educ t ive  and o x i d a t i v e  atmo- 
p h e r e s  on t h e  y i e l d s .  
-3- 
I 
(. 
, Experiment a1 
I n  a t y p i c a l  exFcriment,  a mixture of two milliliters 
of  f r e s h l y  d i s t i l l e d  F y r r o l ,  fou r  m i l i i l i t e r s  of beozafdehyde 
and four m i l l i l i t e r s  of double d i s t i l l e d  xater w a s  p l aced  in 
a n  i r r a d i a t i o n  v e s s e l  (approximately 30 CC. in volume), When 
u s i n g  a r e d u c t i v e  atmosphere,  t h e  vessel W&S connected t o  an  
appa;*atus which aiioweci Eetiiaiie, a o i i i a  sz12 k.,y2rsgen t n  
cone i n  c o n t a c t  w i t h  t h e  c i x t u r e  d u r i s g  i r r a , d i a t i o n .  The p a r t i a l  
pressures of the  gasses i n  the v e s s e l  b e f o r e  i r r a d i a t i o n  were 
8.7 crn of hydrogen, 8,r+ CIC of a m o n i z  and 8,7 cm of  methane 
wi th  t h e  remaining p r e s s u r e  due t o  water a r d  organic  vapors. 
%hen u s i n g  a n  o x i d a t i v e  atmos?here, a watar  cosdljnser w a s  
cornec ted  t o  tfie s ide- t i rm of t h e  vessel. e ' rdinary air en te r9d  
t h e  v e s s e l  th rccgh  t h e  condenser.  A t e s l a - c o i l  ( E l e c t r o  
Technic  Products ,  Chicago, I l l i n o i s )  wns used t o  produce t h e  
e l e c t r i c a l  dischargeo Samples were i r r a d i s t e d  f o r  two and 
f o - i  horn 2 e r i o d s  i n  semi-dsrkness, 
Lft.cr aircfi rus3 t h e  t e z p z r a t u r e  and pE o f  t hd -mix tu re  
w a s  recorded,  The t e s p v a t c r e  of  t h e  rnixtnre v a r i e d  from 
40-60°C, whi.7-e t h e  p-9 var ied  betweer, 4 and 6 .  
of t h e  r e a c t i o n  were t h e n  poured i n t o  a s c p a r a t o r y  funne l  
t o  which w a s  added 25 m i l l i l i t e z s  of water  and t h e  benzene 
washings from t he  r e a c t i o n  vessel .  The funnel was shaken 
and t h e n  l e f t  t o  s t a n d ' u n t i l  a s e p a r a t i o n  o f  t h e  benzene-layer 
The p roduc t s  
- b . 
I - -  
.-* 1 
4 -4- 
e 
from t h e  aqueous-layer was complete. 
p l aced  i n t o  a beaker  charged with 10 grams o f  anhydrous 
The bGnzene-layer was 
sodium sulfatz t o  raroove t r s c e s  o f  xat5r. The s o l u t i o n  w a s  
-.. 
I metric flask, with t h e  use  of a s y r i c g e ,  25 m i c r o l i t e r  
q u h n t i t i e s  o f  t h e  Eraduct were s ; jot ted on th in - l zye r  chro- 
matographic plates having a 250 r n i ~ m r l  t h i c k  layer  of 
dehydrated s i l i c a - g e l ,  The & G t L s  were gldced f o r  two 
hours  into a t%ck  co;itai ,u 'rg 200 m i l l i b i t e r s  of  a s o l u t i o n  
of 2% xylene in benzene, 
A f t e r  t h e  p k t e s  were t a k e n  o u t  o f  t h e  tank and d r i e d  
t h e  porphin2 bands werc scraped  i n t o  long-stem funne l s  
blocked wi th  c o t t o g  Flugs, The porphine was e l s t e d  uith 
benzene and t h e  voltlne cf porphine solution made up t o  3 
nil7.i.liter.s fo r  a11 samples,  
totra,h~-cylporF!ij.iie Sy vis - i .3 l i  spectra of  t h e  f r e e  base  
m Ihe S?ec?ra of u 4 Q  ,y 3 - t e t r eph .~n l i lpo rph ine  a r e a  
reccrdeci cn a Bazsck & Lcnb SpGctronie 5 2 5 ,  an2 t h e  t o t a l  
y i e l d  p e r  50 m i l l i l i t e r  s z p l e  WGS c c l c z l a t e d  from molar- 
e x t i n c t i o n  c o e f f i c i e n t  of 4.78 X 10 5 a t  418 mil l imicrons.  
R e s u l t s  and Discuss ion  
F i g c l  r e p r e s e n t s  t h e  r e s u l t s  ob tz inQd from r u n s i i n  
a r e d u c t i v e  atmosphere, as compared with  rum which occurred 
spontaeous ly ,  i n  presence o f  molecular oxygen. i.e. without  
. 
.-' '1 
4 -5- 
* 
t h e  use of e l e c t r i c a l  d i scharges ,  I t  i s  p l o t  f t o t a l  
y i e l d  i n  ng pssr m q l e  versus t h e  tinie o f  s t o r a g e  i n  days. 
The i n c r e a s e  i n  t h e  y L e l 3  of T?? wi5h t im Inc l ica tes  t h a t  
a p rocess  of a u t o c a t a l y s l s  t z k a s  p l aceo  
postuleted by C31v i2 ,  now can  be  su_npocted by experimental  
ev idense-  The cont inuous chaoge i n  t h a  s l o p e  can  be  expla ined  
by considering t h e  environmentzi  co r l i i l t l o i i i  of  t h e  
experiment,  
r a t e  of formation by z u t o c a t a l y s i s  i s  &ow, as  r e p e m e n t e d  
by t h e  low slope.  The sampic- i n  bcnczne wzs s t o r e d  i n  
c o n t a c t  with air  con ta in ing  moldculzr oxygzn. As t h e  s o l u t i o n  
became s a t u r a t e d  wi th  a i r  the s l o p e  i n c r t x s ; d .  T h i s  i n  t u r n  
i n d i c a t e s  t h a t  molacular oxygen is ntcessary f o r  t h e  r e a c t i o n  
t o  occur.  
This  g rocess ,  
It can be argued t h a t  i n  t h e  beginning t h e  
Fig. 2 r e p r e s e n t s  slmilar r z s u i t s  ob ta ined  from r u n s  i n  
en o x i d a t i v e  atmosphere,  as  compsred wi th  r u n s  which occurred 
spontaneously.  I n  t h i s  ca se  i t  is a l s o  a p l o t  of  t o t a l  yield 
i n  m g  per  s m p l e  v e r s u s  t ime of s t o r a g e  of  t h e  s a m g l e  i n  
benzena. It can be seen that t h e  s l o p e  of t h e  curve, which 
r e p r e s e n t s  t h e  r a t a  o f  formation of Ti?? upon s t a n d i n g  by 
a u t o - c a t a l y s i s  has a cons tan t  va lue ,  because t h e  s o l u t i o n s  
were e q u i l i b r a t e d  wi th  t h e  air, and t h e r e f o r e  t h e  molecular  
oxygen is available f o r  t h e  s y n t h e s i s ,  
Fig. 3 r e p r e s e n t s  supcriapoacd Z i p r c s  1 and 2 and 
unde : r l i n>z  t!ie ? ~ T < ~ : - ~ X S ~ G  i.2 t k e  irlti2.1 d o p e s ,  as dis- 
c u s s a i  p r iv ious iy .  
r each  z p o i n t  hhere  t h e  s ioLJes z r e  t h e  s a e o  
- cen  5t s&:- t L a t  bo th  l i n e s  f i n a l l y  
Fig. 4 r t p r e s e n t s  t h e  a r a e  2102 of  y i - l d  v e r s u s  t h e  
t i m e  of s t o r a g e  for i: samgle, which i ; 3 S  been  e q o s t - d  t o  
f o u r  hours  of e i e c t r i c a i  d i s c h ~ r g e ,  ~i; i  L ~ ~ ~ ' - ~ ~ ~  y v  
h o c r s  for t'ne p r -v ious  three.  slides, 
t h a t  t h e r e  is no i n c r e a s e  i n  t h ;  y i e l d  o f  TPT upon s t x G i n g  
as observed i n  p rev ious  c';'is~'s. The t e n t a t i v e  t;x&lanntioncrf 
t h e  r t ; su i t s  i s  a s  fol lows.  It id suggested t h a t  t 5 e  s y n t h e s i s  
of TPP procezds t h o u g h  t h e  formst ion of  a l ~ b i l z  i n t z r m e d i e t e  
which can  b e  t a s i l y  i ;<stroyed by reLCtion p roduc t s  of the 
e l e c t r i c a l  d i scharge .  
t h e  sarrple t o  e l e c t r f c z l  d i scharge  des t roga  most of t h e  
i n t e r c e d i G t e  2s zg  '? ,y , b - t e t r apheny lch lo r in ,  b u t  t h i s  
- -  - - - - - - - a  +, trsln 
The r e s u l t s  i n d i c a t e  
ApparLntly t h e  fou r  hour exposure @ 
r e q u i r e s  conf i rmat ion .  
I n  conclus ion ,  w e  have shown th;t porphine- l ike  
s u b s t a n c e s  can  be formzd sbiogcnic: l lg  i n  prLsence of 
oxygen and not  t o o  prolongLd e q o s u r e  tow-rd e l e c t r i c 1  
d i scha rges .  The s y n t h c s i s  proce2ds through t h e  formntion 
o f  a n  i n t e r m e d i a t e  , which then  a u t o c z t a l y t i c d l y  changes 
i n t o  t h e  f i n d  product .  
The work was supportc;ii i n  p a r t  by t h e  Grant fSsG-225-62 
from Nat ionnl  Aeronaut ics  and Spzct ACininistration. 
-6- 
. 
I F  
2. 
3 e  
4. 
(3) A.1, C ~ F . ~ ? . . T %  ml;c3 Origin of  L i f e  on t h e  E<arth( t rans-  
- . A L + + ?  1); - L . ~  S;yYge) 3rCw ed., w;-denic P r c s s ,  New Pork 
13-77; (b) L i f e ,  Its Sa tu re ,  Or ig in  and Development 
( t r a n s l a t e d  by A. Synge),  Academic Press, Hew York, 1962 
H.C. Urey, The P l a n e t s ,  Yale Un ive r s i ty  P r e s s ,  N e w  Hzven 
Zoniisztleut, 1952, 
J.B,S. Haldane, C o l l e c t i o n  of Essays on t h e  Or ig in  of 
L i f e ,  Penguin Books, Ltd., Lor-don, 1954. 
(a) S.L.Miller,  Sc ience  117, 528-529 (1953);  (b) J, An. 
Chem. SOC. 22, 2351-2361 (1955) ;  ( c >  A n n .  X.Y. xc?.d.&i. 
9, 260-274 (1957); (d )  Biochim -t Biophys, Acta 3 
480-489 (1957). 
( a )  M. Calvin,  Sc ience  - 130, 1170-1174 (1959) ; (b) Med. 
2. 147-172 (1962). 
I U  
(a) Chem Eng. cws 2 96-104 (Incay 22, 1961);  (b) Per - 
s p e c t i v e s  i n  Biol.  Med. 5 ,  399-422 (1962). 
(a) A. Szutka,  J.F. Hazel and W.M. McNzbb, Rad. Rese.rrrch 
4, 191 (1958),  (b )  Rad. Research l0, 597 (1959) 
A. Szutka, Rad. Research 19, 183 (1963); Nature -9 202 1231 
(196%. 
A, Szutka,  On "The O r i g i n s  of P r e b i o l o g i c a l  Systems", p. 
2&3-54. S.W. Fox, ed,, Academic P res s ,  New York, 1964. 


Porphine-like substances. III - Synthesis by electrical discharge

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