synthesis and reactions of aromatic ethers as model compounds … · 2020. 7. 21. · synthesis and...
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Eastern Illinois UniversityThe Keep
Masters Theses Student Theses & Publications
1983
Synthesis and Reactions of Aromatic Ethers asModel Compounds for CoalJames Nicolas Ong SyEastern Illinois UniversityThis research is a product of the graduate program in Chemistry at Eastern Illinois University. Find out moreabout the program.
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Recommended CitationSy, James Nicolas Ong, "Synthesis and Reactions of Aromatic Ethers as Model Compounds for Coal" (1983). Masters Theses. 2855.https://thekeep.eiu.edu/theses/2855
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m
SYNTHESIS AND REACTIONS OF AROMATIC ETHERS
AS MODEL COMPOUNDS FOR COAL (TITLE)
BY
JAlVIES NICOLAS ONG SY
THESIS
SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE IN CHEMISTRY
IN THE GRADUATE SCHOOL, EASTERN ILLINOIS UNIVERSITY CHARLESTON, ILLINOIS
YEAR
I HEREBY RECOMMEND THIS THESIS BE ACCEPTED AS FULFILLING THIS PART OF THE GRADUATE DEGREE CITED ABOVE
/\ n\/IC'CD
?f-1- Y> DATE COMMITTEE MEMBER
DATE 'f "COMj.# 1nff MEMBER r} ) ", ·2 -(,. - - .::. "'
J- /- J>? DATE • DEPARTMENT CHAIRPERSON
SYNTHESIS AJ\1D REACTIONS OF ARCMATIC ETHERS
AS MCDEL COMPCU1\1DS FOR COAL
Jame s N i c olas Ong Sy, Mas te r of S c ience , Augus t 1 983
The s i s d ire c te d by Dr. David H. Buchanan
.ACK!\ OWIEDGEIV:ENT
My sincerest appreciation is hereby extended to my Researc�
.Advisor, Dr. David H . Buchanan, whose assistance and guidance
during the entire project have been invaluable.
.-·
D:E:DICATICI\
This piece of work is lovingly dedicated to my family,
specially to my parents, whose love, support, encouragement
and care made this project possible.
This work is also dedicated to our Almighty God:
'I'hy word is a lamp unto my feet and a light unto my path.
-Psalm 119 : 105
Intr oduc ti or1
Experimental
Re sults
D i s c ussion
Referenc e s
TABIE OF CONTENTS
. . ------------------------------
Page
1
7
39
44
59
ABSTRAC'I'
o-Anisic acid and o-ethoxybeRzoic acid were reacted with
pyridine hydriodide in pyridi�e at 115° for 3 days to yield
81% and 18}; salicylic acid respectively. o-Anisic acid with
KI in pyridine at 115 ° for 3 days gave 58% salicyl�c acid
while o-anisic acid with LiI·3H2o in pyridine at 85° for 3 days
gave 54% salicylic acid. p-Anisic acid and o-phe�oxybenzoic
acid did not u�dergo cleavage reactions with pyridine hydriodide
under similar conditions.
Beta-methylnanhthyl beta-naphthyl ether(I) or alpha
methylnaphthyl alpha-naphthyl ether(II) with pyridine hydriodide
in pyridine at 1 0 0-115° for 3 days showed no cleavage. Ether I
with pyridine hydriodide in the presence of pyridine insoluble
Illinois No.6 coal fraction at 115 ° for 7 days or with added
iron salts, such as FeC12, FeS and FeS2 also showed no cleav
age. Recovered ether averaged 98 ± 3%.
Since pyridine hydriodide or lithium iodide in pyridine
increases the free phenolic conte�t and reduces the apparent
molecular weight of pre-asphaltene fraction of Illinois No.6
coal, presumably by ether cleavage, the coal structures react-
ing are not well-modeled by ethers I and II. It is proposed
that oxygen atoms of the reacting ether linkages in the coal
fraction are hydrogen bonded by phenol groups either on the
same or adjacent aromatic-cluster which activates them toward
S�,2 cleavage by iodide io1' under mild conditions l�
INTROD�l CTI ON
Studies suggest that coal is composed of macromolecular
units linked together by oxygen bonds. Ruberto1 deduced
from salvation studies of coal that it appears to consist
primarily of 2- and 3- ring condensed aromatic structures
linked mainly by oxygen atoms. Takegami2
concluded that
the formation of asphaltenes from mild hydrogenation of bit. uminous coal is due to cleavage of ether linkages. Wachcwska3
noted that while the extent of ether linkages varies widely
with coal rank, ether groups represent the main linkages
between aromatic clusters. It is believed that the single
bonds in coal most likely to be broken and assist its lique-
f t. d "l' d"t" 4 ac ion un er mi a con i ions are :
Ar-CH -Ar 2 Ar-0-Ar
Ar- ( CH2 ) n-Ar R-0-Ar
Ar-CH2-0-Ar
R-0-R
and sulfur analogs
where: Ar = aryl groups R = aliphatic groups
The connecting ether linkages in coal have be en the
subject of several studies. Different cleaving agents and
reaction conditions were used to break these bonds in coal
and in model compounds.
A model compound is one whose atomic configuration is
responsible for coal-like behavior and might be a component
of the hypothetical coal molecule5. Studies on model compounds
are conducted to give a better insight of the structure inside
the coal and the connecting linkages responsible for this
2
structure. Hydrogenolysis of coal-related model compo:mds
by a CO-H2o mixture at 300° were conducted and cleavage was
found to occur readily6
.
Model Compounds
Benzyl phenyl ether
Phenyl ether
Benzyl ether
Products
Benzene, toluene
Benzene
Benzene, toluene
ZnC12 has also been used to effect cleavage on model
compounds?:
Model Compounds
Benzyl ether
Phenyl ether
Benzyl phenyl ether
Benzyl naphthyl ether
The post�lated mechanism:
rnCl2 @CHz-�-© �
Products
Diphenyl methane
No reaction
Diphenyl methane
Diphenyl methane,
Beta-naphthol
@�HL + [@0��znc12] <Q>--cH2-© + ft+
@oH + lnC'I,_
3
When c oal i ts e lf was trea te d wi th K/TEF in the pre sence
of naph thalene f o l l owe d by quenc�inr wi th di lute HCl, i t was
f ound that th:re was a s ubs tantial incre ase in the hydroxyl
c onte nt and flui d i ty of c oa1 8 . The se re s ults were c onsi s tent
wi th the c le avage of e ther b onds .
The me chani sm o f the reac t i on may be :
0 • + K+ K + C10H8 --.:;:> (C10H8)-.1
(Ar -0-Ar ) ..!.. + Ar-0-Ar + (C10H8) --� C1c}13 (Ar -0-Ar ).!.
__ ..,,. Aro + Ar· .
Ar · + (C10H8)- --7 Ar + C10H8 Ar +HOH --� ArH + OH Aro +HOH --� Ar OH + OH where Ar-OAr repre s e nt s d iaryl e ther linkage s ,
Sod i um in l i quid ammonia ac t s in a s imi lar manne r when c le av-
ing e ther linkage s
le fragment s 9 : Na
Ar-0-Ar ----- 7 l i q . NHJ
Na Ar• ---?> Ar-
Ar o H
--?> s olv
Ar OH
in c oal, re sulting in smalle r, more solub -
(Ar -0-Ar).!.
H --� ArH s olv
_ _ .,.. Aro + Ar .
C oal c ons i s ts of s e ve ral fracti ons which e xhibi t c ontra s t -
ing s olub i l i tie s i n d ifferent s olvents:
4
E xtrac te d c oal
Pre -aspha ltene ( Asphal t ol)
Asphaltene
Oi l
S oluble in
None
Pyrid ine
Toluene
H exane
Ins oluble in
All
Toluene
Hexane
Proti c s olve nts
Whe n Mayo e t a11 0 reac te d an asphal t ol frac ti on of Ill i
noi s N o.6 C oal wi th Na/liq. NHJ f ol l owe d by quenching wi th
NH4c1, there was obs e rve d a d e crease in mole c ular we igh t and
incre ase in the phe nolic - OH c ontent of the c oal frac ti on .
S imi lar obs e rvati ons were note d by reac ting the asphaltol
frac ti on wi th pyrid ine hydri odide at 20°. Whe n the y c onduc ted
the reac ti on at 50°, the y f ound that the mol e c ular we ight of
the c oal frac ti on was re duc e d t o the same extent as with Na/liq.
NH3 . Cle avage of e the r linkage s would e xp lain the s e re sults.
Pyridine hydri od i de has be e n we l l - s tudied. Odinok ov1 1
c onc lude d from h i s infrared and NMR s t ud i e s of pyrid inium
salts , tha t f or s tr ong ac idslike H I ( pKa = -1 1 ), prot on trans
fer wi th pyridine take s p lac e and the "i oni c pair" i s the
pre d ominant spe c i e s . A hydrogen b onding enthalpy of - 6 . 7
kcal/mole re sults from the s a l t f ormati on . Thi s "ionic pai r "
i s c onfirme d b y the pre s e nc e of N -H s tre tch ing fre quency maxima
a t 2 83 3 cm- 1 in the infrare d spe c tra .
R oye r e t al1 2 has used pyridinium halide salts in e the r
c le avage reacti ons� - The y f ound that pyridine hydrogen bromi de
c le ave d alkyl naphthyl e thers at 23 0°. Chen1 3 f ound that whe n
phenyl alky l e thers and e s te r s we re reac ted wi th pyrid ine
hydri od ide at 6 0 - 8 0 ° , no s i gnificant e ther or e s te r c le avage
5
wa s obs e rve d . A t 2 1 0° , she f ound tha t pyridine hydri odide
c le ave s phenyl e thers and e s te r . The l owe r temperature re s ults
wi th mode ls c ontras t wi th the c oal reac t i ons .
C le avage Reac ti ons wi th Pyridine Hydri odide at H igh
Temperature ( re ac ti on time : 45 h our s , reac ti on temp . : 2 1 0°)
Ether or E s te r
Ani s ole
B e n zyl phe nyl e ther
Cyc l ohexyl phe nyl e ther
Me thyl benz oate
Phenyl phe n ( e thyl) ether
Produc ts
Phenol
Phenol, tolue ne
Phenol
Benz o i c ac i d
Ethylbenzene, phenol
Lar s e n1 4 c onduc te d a reac ti on which s e l e c tive ly labe l e d
the - OH groups in c oal wi th tri-n-butyltin and u s e d Mos sbauer
spe c tr os c opy t o de duce inf ormati on ab out the he teroa t om p op
ulati on ne ar the hydroxyl group. He reacted I llinois N o . 6
C oal wi th b i s ( tributyl ) ti n oxide in refluxing to luene . The
tin Mos sbaue r spe c trum of the c oal derivative showed that
almos t all of the tin i s in trig onal b ipyramid f orm . N o
evidence was f ound f or the pre s e nc e o f te trahe dral tin . Th i s
c an only b e true i f a ne arby atom wi th an unshared pair of
e le c tr ons can enter into the c o ordinati on she ll of tin . Thi s
he te roatom mus t b e suffi c iently c l o s e f or i t t o s e rve a s an
acce ptor for a hydroge n b ond from the now de rivati z e d hydr oxyl .
I n other words , almos t all of the -OH in I llinoi s N o. 6 C oal
may�hydr ogen bonded to an o ther he te roatom wi thin the s olid .
6
If thi s i s the case , the fir s t s te p in ether c le avage, that
i s , the pr otonati on of the e the r oxyge n , may n o t re quire an
e xte rnal pr o ton s ource ins ide the c oal because the e ther
oxygen is alre ady in hydrogen b onde d form . In c oal , a ttac k
by the i od i d e ion o n the carb on ad j a c e nt to the e the r oxygen
maybe s uffi c ient for c le avage and thus the obs e rved re duc ti on
in the m ole c ular we igh t of c oal . Thi s internal pro t onati on
c ould we l l exp lain the reac ti on of the asphaltol frac ti on of
c oal wi th li th i um i od ide . Mayo e t a11 0 obs e rve d that Lil,
a reagent that d oe s not have a pro t on s ource, i s e qually
e ffe c tive as pyridine hydri odide in re duc ing the mole c ular
we i ght and incre as� the phenolic -OH c ontent of c oal .
Thi s the s i s c overs the f ol l owing areas :
1 . An e x tenti on of Chen's work wi th mode l c omp ounds . That
i s , synthe s i s of various naph thyl e the rs and the s tudy of
the ir reac ti ons wi th pyridine hydri od ide and other agents.
2. In line wi th Lars e n's re s ul t s , a s tudy of c le avage reac t
i ons of o -ani s i c ac id and p-ani s i c ac id wi th pyrid ine hydr
i odide , Li I · JH20 and other c le aving agents . The former ac i d
h a s i ts e ther i n hydrogen b on d e d form wh ile the la tter d oe sn't,
J . A s tudy of naph thyl e ther reac ti on wi th pyridine hydr
i odide u s i ng c oal as c atalys t . The reas oning i s that , the
environment ins ide the c oal migh t promote e ther c le avage .
7
EXPERIMENTAL SECTION
Gene ral
NMR spe c tra were ob taine d on a Vari an T-6 0 nuc lear mag
ne tic re s onanc e spe c trome ter us ing te trame thyls i lane(TMS) a s an
inte rnal s tandard . Infrare d spec tra were re cord e d by a Perkin-
E lmer 33 7 grating infrared spe c trophotome ter(calibrati on peaks
at 1 6 01 and 1 0 28 cm-1) . Mas s spe c tral analyse s were c ond uc ted
on a Du P ont 2 1 -4 9 0 mas s spe c trome ter. HPLC analyse s were
d one on a Be ckman Mode l J42 Grad i e nt Liq uid Chromatograph
sys tem , re tenti on t ime s and are a meas urementswere re c orde d
by a Shimad z u Chromatopac C -RlB. The c olumn us e d f or the
HPLC was 4 . 6 mm x 1 5 cm c 1 8 reve r s e d pha s e . Identitie s of
the de s ire d pe aks were base d on c ompari s on of re tenti on time s .
Me lting p oints were taken on a Thomas -H o over cap i llary melting
p o int appara tus and are re p or te d unc orre c ted . Pre -inje c ti on
c le an - up of HPLC samp le s was c e n trifuging on a Beckman M i c r o
fuge ™ 1 1 at 1 1 , 0 0 0 rpm. S e p -pak u s e d f or analytical c le an - up
of c oa l -cataly z e d reacti ons i s a c 1 8cartri dge purcha s e d from
Wate rs A s s oc iate s . Carbon and hydr ogen analyse s were d one
e ithe r a t the Unive rs i ty of I llino i s or Mi c Anal Organic M i c r o -
analys i s Lab oratory .
Pyridine hydri od ide u s e d was previ ous ly pre pare d by
Che n13(m.p . 2 1 1 - 2 1 4 ° , Che� 's reporte d m.p. 212 - 2 1 4° , li t . ,
2 1 4 °)1 5 . The c oal u s e d was the e xtrac ted c oal p orti on(pyrid ine
ins o l uble frac ti on) of C oal FSOC 25 2(Penn S tate Coa l Data Bank)
prepare d by Ballard16 and has the f o l l owing DAF e lemental
analy s i s : C , 74 . 01% ; H , 5 . 2J% ; N, 2 . 0J % ; O + S, 1 8.7J %(by d i ff -
8
erenc e ) .
Pyrid ine was p urchase d fr om Fi she� S c i entific C ompany
and was d i s t i l le d ove r BaO , the n kept in a r ounqb ottom flask
cappe d wi th a rubbe r s e ptum t o ke e p it anhydrous. The HFLC
water use d was d i s tilled de i o�ize d wate r that was pas s e d
through 45 mi c r on fi l ter purchase d from Mi l l ipore C orporati on.
Me thano l and ac e toni tri le were HPLC grade s olvents purcha s e d
from J.T. Baker Chemi cal C o . . o -Ani s i c a c i d , o -phenoxybenz oi c
acid, o - e thoxybenzoic ac id , bibenzyl , hydr oc innami c acid , te tra
b utyl phosphon i um bromi de , a lpha - and be ta - me thylnaph thalene
were purchas e d from A ldri ch Chemic a l C ompany . p -Ani s i c ac i d ,
hydr o i o d i c a c i d , phthalic ac i d and p -hydroxyben z o i c ac id were
p urchas e d from Eas tman Organic Chemi cals. A lpha-naphthol , be ta
naphthol were purcha s e d from Fis cher S c i e ntifi c C ompany .
Li I · JH20 was purcha s e d from A lfa Divi s i on. A l l we re reage nt
grade che mi cals and us e d wi thout further purif i cati on .
9
?re�araticn of AlDha ard Esta Eromomethvlna�hthalene via
Photobromination:
The me thod of Chapman and Williams was us e d17 . Beta-
me thylnaphthalene (l00.00 g, 0.70 m o l e s) in cc14(JOO mL) was
put in a 1-L, J-ne ck r ound bottom flask e quippe d wit.h a mag-
netic stirrer, cond e ns e r and gas trap. Bromine (27.00 g, 0.17
mole s) in cc14(JOO mL) was adde d dropwise during a 6-hr pe riod
to the stirre d s o lution of be ta-me thylnaphthalene in r eflux-
ing cc14 and irradiate d with a 500-w tungsten bull: 2 inche s
fr om the fla sk. Afte r the evo lution of HBr gas had c e a s e d,
the re action mixture was s tirre d at reflux f or ano ther 2 h ours.
cc14 was rem ove d by s imp le distillation and the re sidue was
fractiona t e d at 5 mm Hg to rem ove the unre ac te d be ta-methyl
naphthal e ne (b. p. 98-102°/5 mm) to give 75.80 g(75.80% re c ove ry).
The crude be ta-br omomethylnaphtha lene wa s obtaine d by c ontin-
uing the vac uum dis ti l lation and c o lle cting a frac tion at
118-12J0/1.2 mm. The crude pr oduct was purifie d by r e c rysta l
liza tion from h o t e thano l t o give JO.JS g(81% yie ld). (M.P.
52.5-54.0°, lit., 54°)17. NMR(CDClJ) Chemic al s hifts, ppm:
7 . 8-7. 2 ( m, 7 ) ; 4. 5 ( s , 2 ) . IR ( KBr) : J 0 5 0, 2 9 5 O , 16 O O, 15 0 O, 14 O O ,
4 -1 1208, 818, 7 O c m .
Alpha-br omomethylnaphtha l e ne was pr e par e d in the same way
exce pt the starting reagent was alpha-me thylnaphthalene .
Alnha-bromome thylnaphthalene (m.p. 5J.5-55.0°, lit., 56°)18 ..
NKR (CDCl�) Chemical shifts, ppm: 8.2-7.2 (m,7); 4.9 (s,2). _,
IR (KBr) : J050, 2960_, 1590, 1500, 1400, 1.196, 760 c m-1 .
10
Preparati on of Ar omatic Nanhthvl Ethe rs I to I V .
Ethe r
I
I I
I I I
IV
Name
Beta -methylnaphthyl
be ta-naphthyl e ther
Be ta -me thylnaphthyl -
alpha -naphthyl e ther
A lpha -me thylnaph thyl -
�lpha -naph thyl e ther
Alpha -me thylnaph thyl'-
be ta -naphthyl e ther
S tr uc tur e
00- c"2o(o)O) (QfgCH2�
g-c�,O-oo The me thod of D 'Incan and Vi out1 9 was use d . Beta�naph
thol ( 1 2 . 78 g , 0 . 0 8 9 mole s) in me thylene chloride ( 2 0 0 mL) was
put in a 5 0 0 -mL , J-neck , round b ottom f lask e quippe d wi th a
magne tic . s tirrer and condense r . NaOH ( J.55 g , o. 0 8 9 mole s) in
40 mL H2o was add e d to the f lask . The r e ac t i on mixture was
stirred a t r o om tempe rature f or JO min . . Beta -bromome thyl
naphthalene (14. 0 0 g , 0 . 063 mole s ) was adde d to the f lask
f ol l owed by te trab utyl phosphonium bromide as phase transf e r
catalyst. The reaction mixture was stirred at room temre rat
ure f or 24 hours. The final solutio� was acidified to pH = 3
v1i th 2Ci% HCl, the layers serara ted and the water layer extract-
11
ed wi th 3 x 1 0 ml CH2c12. The organi c layers we re c ombine d
a:r:d washed with 20 rr.L cf 5% I\aCH aEd 1 x 10 mL H2c. 'I'he
soluti on was dri e d wi th anhydrous Na2so4, pas s e d through a
plug_ of gla s s wool and the s olvent remove d on the rotary
evaporat or. The crude produc t was puri f i e d by re c ry stalli z -
ati o� from hot e thano l . NMR, IR and mas s spe c tra of ethers
I to IV are sh own in Figure s I to XI I.
Ether
I I I I I I IV
Yie ld ( %) 2 1 9 1 8 6
NMR Chem. Shift ( ppm) ( m , 14 H) 8,0 -7.0 8 . 4 -6,7 8.3 -6 . 8 8 . 0- 7 . 0 ( s , 2 H) 5 . 5 5,4 5 , 6 5 , 5
Mas s Spe c trum ( m/e) Parent peak 2 84 284 284 284 Base peak 141 141 1 4 1 141
- 1 IR S pe c trum ( cm ) 3 08 0 3 04 0 3 04 0 3 04 0 2 93 0 292 0 2 93 0 2 95 0 15 85 1 5 70 1 5 8 0 1 6 0 0 1 45 0 1 3 7 0 1 3 6 0 147 0 1 25 8 1 2 6 0 1 2 63 1 25 0 1 2 1 8 1 23 0 1 23 8 1 2 0 8 1 0 03 1 06 0 1 06 9 993
Elemental Analys i s
The ore tical c 8 8.7 0 8 8 . 7 0 8 8 . 7 0 8 8 . 7 0 H 5,67 5 ,67 5 . 6 7 5,6 7 0 5 . 63 5 ,63 5 . 63 5 .63
Ac tual c 88.36 88.64 87 . 92 88.28 H 5 ,37 5.42 5 . 7 7 5 . 77 0 ( d i ffere nce ) 6.27 5 ,94 6 . 31 5 . 95
1 2
S tandard i zati on of Naphthyl E ther I and Be ta -naph th ol with
Bibe nzyl f or Quantitative Analys i s o f Reac ti on Mixture s .
Naphthyl e ther I ( l O . O mg) and be ta-naph th o l ( l O . O mg) were
we ighed into a 25 -mL volumetric f lask and d i lute d to volume
with ace t onitri le to give a s tock c onc entrati on of 0 . 4 0 0 mg/mL.
In a s eparate 1 0 0 -ml v olumetri c f lask , b i benzyl ( 2 . 0 0 0 0 f was
we ighed and di lute d to volume with acetonitri le to give a
stock c onc entrati on of 2 0 . 0 0 mg/mL . For standard 1 , 2 ml of
naph thyl e ther I + beta -naphth ol stock s oluti on was mixe d wi th
1 mL of the bibenzyl stock s oluti on. For standard 2 , 1 mL of
naphthyl e ther I + beta-naphth ol stock was mixe d with 1 mL of
the bibenzyl stock s oluti on . The bibenzyl i s an internal
standard whi le beta-naphth ol i s one of the expe cte d c leavage
pr oducts .
The two standards were c e ntrifuge d , inje c te d into the
HPLC and the re lative are as re c orde d. Duplicate runs of e ach
s tandard were d one and the re lative are as ave rage d . From the
re lative are as and known amount of materials us e d in calibrat-
ing , the dete ctor re s p onse factors were de termine d .
Naphthyl ether II I was c alibra te d in a s imi lar way.
S tandard i zati on of Naphthyl Ether I and B-e ·ta-naph thol with
Naph thale ne f or Quantitative Analys i s o f Phe nyl S ulfide -
Catalyze d Re ac ti o� _ Naphthy l e ther I ( 2 0 . 0 mg) and �naph th ol ( 2 0 . 0 mg) were
weighe d int o a 25 -mL volume tr i c f lask and d i lute d t o volume
with ac etoni tri le to give a stock c or:c entrati on of O. 8 0 0 mg/ml .
13
l!'l a se pa:ra te 1 C-rr.I. volu.me tri c flask, napt-'chalene ( 1 0. 0 mg)
was weighed and dilute d to volume with a c e tonitrile to give
a stock conc entration of 1.00 mg/mL. Standard 1 was pre pared
by mixing 1 mL of beta-naphthol + naphthyl ether I stock
solution with 1 mL of naphthale ne stock, while standard 2
was pre pare d by mixing 2 mL of naphthyl ether I + beta-naphthol
stock with 1 mL of naphthalene stock. These 2 standards were
c e ntrifuge d and calibrate d on the HPLC.
S tandardiza tion of o-Anisic Acid and S alic ylic Acid with
Hydrocinnamic Acid for Quantitative Analysis of Cle avage
Re actions.
o-Anisic acid(25.0 mg) and s alic ylic acid(25. 0 mg) we re
weighe d int o a 25-mL volumetric flask and dilute d to volume
with 1, 2-dic hloroethane t o give a stock conc entration of 1.00
mg/mL. In anothe r 50-mL volume tric flask, hydrocinnamic acid
( 3 0 0 . 0 mg) was weighed and dilute d to vo lume with 1,2-dichl oro
e thane to give a s to c k conce ntratio� of 6.oo mg/mL. For
s tandard 1, 1 mL of o-anisic acid + salicylic acid s tock
solution was mixed with 1 mL of hydrocinnamic acid s t ock
solution, while 2 mL of o-anisic a cid + salicylic acid s tock
was mixed with 1 mL of hydr o cinnamic acid s tock t o make stand
ard 2. The s e 2 s tandard s were c entrifuge d and us e d to calib-
rate the HPLC.
In a s e cond c al i b ration, o-anisic acid ( 1 0.0 mg) and
salicylic acid(10.0 mg) were weighed into a 25-mL volumetric
flask and diluted to volume with 1,2-dichloroethane to give
a stock conc entration of 0.400 mg/rr:L. Hydrocinnamic acid
(350.0 mg) was weighed into a 50-mL volumetric flask and
14
dilute d to volume wi th 1 ,2- d i c hloroethane to give a stock
concentration of 7,00 mg/mL. Two ml· of o - anisic acid + sal-
icylic aci d st ock was mixe d with 2 mL of hydrocinnamic acid
st ock to make standard 1, while 5 mL of o - anisi c acid+ sal-
icylic acid stock soluti on was mixed with 2 mL of hydr oc innam -
ic ac id st ock to make standard 2, These standards were c e nt-
rifuged and use d to c alibra t e the HPLC.
Standardizati on of p-Anisic Acid and P-Hydroxybenzoic Acid wi th
Hydrocinnamic Acid for Quantita t ive Analysis of Reactions.
p-Anisiq acid(25.0 mg ) and p-hydroxybenzo ic ac id ( 25.0 mg )
were we ighe d into a 50-mL volumetric flask and diluted to '
volume wi th 1,2 -d ichlor o e thape t o give a stock conce ntra t ion
of 0.500 mg/mL. In another 50-mL volume tric flask, hydrocinnam
i c acid(JOO. O mg) was we i ghed and dilute d to volume wi th 1,2-
dichloroe thane to give a stock conce n tra tion of 6.000 mg/mL .
For standard 1 , 1 mL of p-anisic aci d + p-hy droxyben z o ic acid
stock soluti on was mixe d with 10 mL of hydrocinnamic acid
st ock solution , while 2 mL of p- anisic aci d + p -hydroxyb e n z oic
acid s to c k was mixe d w i th 10 mL of hydrocinnamic aci d stock t o
make standard 2. The se standards were ce ntrifuge d and use d •
to calibra te the HPLC.
Standardization of o -Ethoxybenzoic Aci d and Salicylic Acid wi th
Phthalic Acid for Quan t i ta t ive Analysis of Cle avage R e actions.
o-Ethoxybenzoic acid(44.4 mg) and salicylic acid ( 40 . 0 mg)
were we1ghe d into a 10-mL vol umetric flask and dilut�d t o
volume with 1 , 2-d ic hlor oe thane t o give a stock concentration
of 4. 44 and 4. 00 rr,g/mL re spe c ti ve ly. Iodoethane ( 160. 2 mg)
was weighed in to a sep'ara te 10-mL volumetric flask and dilut ed
15
t o volume w i th 1 , 2 -d ictloroe thane t o give a s tock c onc entra t-
i on of 16.02 mg/mL. In an other 100 -ml v o l ume tri c flask ,
phthalic ac id ( 2 0 0.0 mg) was we ighe d and d i lute d to volume
wi th me thanol to give a s tock c onc entra t i on of 2.0 0 0 mg/mL.
F or s tandard 1 , 1 mL of o - e th oxybenz o i c ac id+ salicylic ac id
s t ock s oluti on was mixed wi th 2 mL of i o d oe thane s tock and 1
mL of phthal i c ac id s t oc k s oluti on , while f or s tandard 2 , 2
mL of o -e thoxybe nz o i c ac id + salicylic acid s tock , 4 mL of
i od oe thane s t ock and 1 mL of phthalic ac id s tock was mixe d.
The se 2 s tandard s were c entrifuged and use d to calibrate the
HPLC .
S tandard i zation of o -Phenoxybenz oic Ac id and Sali cylic Acid
wi th Phthalic Acid f or Quanti tative Analys i s o f Reac t i ons,
o -Phenoxybenzo ic ac id ( 5 0 . 2 mg ) and salicylic ac id ( 5 0 . 2
mg) were we ighe d into a 25 -mL volume tric f lask and d i l ute d
t o volume wi th e thyl e ther to give s tock c onc entrati on of
2.01 mg/mL. The phthalic ac i d use d was prepare d ab ove and
has a s tock c onc entrati on of 2 . 0 0 0 mg/mL . F or s tandard 1 ,
2 mL of o -phen oxybenz o i c ac id+ sali cyl i c ac i d was mixed wi th
2 mL of ph thalic ac i d s tock , while 5 mL of o -phe noxybenz oic
a c i d+ salicylic ac id s t ock was mixe d wi th 2 mL of phthali c
ac i d s tock t o make s tandard 2 . The se 2 s tandard s we re cent
rifuge d and us e d t o calibrate the HPIC .
A ttempte d C le avage of Naphthyl Ethers I and I I I wi th Pyridine
Hydri odide and Other C le aving Agents at Low Tempe rature .
The pr oce dure f or a l l e ther reac t i o�s at l ow tempe ra ture
are s imi lar . Var iati ons in the c l e aving agent employe d , reac t
i on time , re ac ti on tempe ratu1-eand c onc entrati on of the c leav-
16
ing agent are noted in the d i s c us sion se c ti on . A repre sentat-
-ive reac ti on i s d e s cribe d here:
Naphthyl e ther I ( 5 0.0 mg , 0.17 6 mmol ) , pyridine hydri odi de
( 6 2.1 mg, 0 . 3 0 mm ol ) in 8 mL pyrid ine were place d in a 25 -ml
round b o t t om fiask e quippe d wi th a ni trogen atmosphere, re flux
c ondens e r and magne t i c s t irre r. The reac ti on was run at 10 0°
f or 3 days . A t thi s p oint , a ye l l owi sh s oluti on was observe d .
The c oole d reac ti on mixture was the n p oure d into 7 0 mL of 1 M
H 2so4 unti l the pH = 2 and n o pyrid ine od or was de te c ted. I t
was extrac te d wi th 3 x 10 mL of e thyl e ther and the c ombined
organic extrac ts washed w i th 1 x 10 mL brine s oluti on and
f i ltered . B ibenzyl ( 2 0 0.0 mg) was we ighe d and adde d t o the
s olu ti on as internal s tandard . The mixture was shaken and
a 1 -mL aliquot was take n , c entrifuge d and HPLC analys i s d one.
The e lu ting s o lvent f or the HPLC was 85% ac e toni tri le/
9 . 5% H20/0 . 5% ac e ti c ac id . The flow rate was 0 . 8 mL/min .
I n j e c ti ons cf 2 0 -mi c r ol i te r or 10-mi c r o li te r ( to ke e p the peaks
ons cale ) sample was used per run. The de te c tor was a Be ckman
M ode l 15 3 Analytical UV D e te c tor.
F or the phe nyl sulfide - cataly z e d c leavage reac ti on, the
e luting s olvent f or the HPLC was 60% ac e t oni tri le/3 8% H2 o/
2% ace ti c ac i d.
Naphthyl Ether I Re ac ti ons in the Pre senc e of a C oal Frac ti on .
Naph thyl e ther I ( 5 0.0 mg,0,176 mmol) and pyridine hydr
i ocide(62.1 mg , O.J O mmol) in 10 ml p�rrid ine we re plac e d in
a 25 -mL r ound b o t t om f lask e quippe d wi th a re f l ux c ondens e r ,
magne t i c s tirrer and c onne c te d via a thre e -way s topcock to
a ni tr oge n line and an aspirator vacuum. Ex trac ted c oa11 9
17
(500.0 mg) was added s lowly to the surface of the pyridine .
_;.spira to2:' vacu0.In was ger;tly applied a:nd -.:hen slowly released
to nitrogen atmosphere . This process was repeated 5 times,
to insure the coal was thoroughly wetted by the solvent . The
0 temperature was then brought to 110 and the reaction allowed
to run for 7 days under nitrogen atmosphere,
After the reaction time, the reaction m i xtur e was allowe d
to cool under nitrogen to room temperature, It was then poured
into 70 mL of 1M HC l and extracted with 4 x 12 mL of ethyl ether .
'Ihe organic extract was allowed t-o pass through a plug of
glass wool. The combined extract was transferred to a sep-
aratory funnel and wasred with 2 x 10 mL of 1M HCl, then with
1 x 10 mL brine solution and then diluted to volume in a 50-
mL volumetric flask. A 1 -mL aliquot was pipetted and passed
through a c18 Sep-pak and 3 mL acetoni trile used to wash the
Sep-pak, all 4 mL was collected. Bibenzyl(10.0 mg) was weighed
and added to the aliqout as internal standard. The sample was
centrifuged and HPLC analysis conducted. The total weight of
the material in the reaction mixture is found by multiplying
the weight found in the aliq UPt by a factor of 50,
Reactions of o-Anisic Acid, p-Anisic Acid, o -Ethoxybenzo ic
Acid and o-Phenoxybenzoic Acid with Pyridine Hydriodide or
Other Cleaving Agents.
The pr oce dure for the se cleavage reactions is s imi lar
to the one employe d for the naphthy l ether reactions,·- howe'\rer
the following changes should be noted. The extracting solvent
was 1,2-dichloroethane or ethyl e the r, the internal standard
was either hydrocinnamic or phthalic acid, the HPLC eluting
18
s olvent for o- , p -ani s ic ac id was 40% me than ol/5 7% wa ter/2.5%
ac e tic ac id. For o -phe noxybe nz oic ac id, i t was 5 0% me thano l/
47.5% wa ter/2.5% ac e tic acid whi le i t was J5% me thanol/61.8%
water/J .2% ac e ti c ac i d f or o - e th oxyben z o i c ac id,
o -Ani s i c ac id ( 26 . 6 mg , 0 . 1 7 5 mmol) , pyridine hydri odide
( 6 2.1 mg , O . J O O mmo l ) in 1 0 mL pyridine were plac e d in a 25-
mL r ound b o tt om f las k , the f lask being under ni tr ogen atmos
phe re and e quipped wi th re flux c ondens er, The mixture was
heated at 85 ° f or J days . The work-up follows that of the
naphthyl e ther I re ac ti on. Hydroc innamic ac id ( J O O . O mg) was
use d as internal s tandard.
In s ome of the experiments , a modifi cati on of the work-up
was c arried out, The c ombined organic extrac t was di luted to
v olume wi th 1 , 2 -d i ch lor oe thane in a 5 0 -mL volume tri c flas.k.
A 1 0 -mL aliquot was pipe t te d out , hydroc innamic ac id ( J 2 . 0 mg)
was we ighe d and add e d t o the aliquot. The t o tal we igh t of the
material to be analy z e d was f ound by mul t iplying the we ight of
the material in the aliquot by a fac t or of 5,
---- . 1 · - .---r-
� 00
} _/ . .!I. r � - ·I'' V" .,,.,., ,...,...'"_ .,.//
8.0
- --- - r-··---- t
I \ •
I _I I i I I ' \ '
I
I;.,: 1 / I ' I I ·!
\ 11r�i 11 i\J�I\
/ /
/
. I L , 1. I ·!\ f; \I I' j ' i : I V . 1 1 11:, :· I 11
1 I \
400 300 200 100
/_,,,---/------- _,I
,-- Jl .- , ... ., ' �· ....... : '1 ,.'\" ', �' . ,. �.�\A../\; .
J --·
·,1.0 . 6.0 5.0 PPM (a) 4.0 3.0 2.0
Figure I nmr spectrum of Naphthyl Ether I
(Beta-methylnaphthyl }?Q_t_9:-naphthyl p·ther)
1 9
).0
I 0 HT
>-H)-
0
SOD
I i\1 I
/\�)i· //
8,0
400 300 200 100
� I l _,./------/ /
--�----------
.I I / I
\.tfV(
'7.0
v�������tfl·
6.0 s.o PPM ( i l 4.0 3.0 2.0
Figure II : nmr spectrum of Naphthyl Ether II
(Let§:_-methylnaphthyl alph§.-naphthyl ether)
20
1.0
0 H•
>-H)>
n
I �00
, r
) ./
-!/ ""''
8.0
!�I \ '
I , I ''
/
I 400 300 200 100
!/�·
v/
\. II i:' ::' 1,
r � (�! \ .. ,··!
.7.0 6.0
FLcr-ure III
·��-'vj�
5.0 PPM ( 6) 4.0 3.0 2.0
nmr spectrum of Naphthyl Ether III
(A1£b.§.-me thy1naph thyl 3]:.p]}�.-naph thy1 F· ther)
21
0 HI
>-H).
,�___.
1.0 0
I 500
/1 I I
rj I, ' : 1 .J i \ 1; " I 1!, ]1 ·. j '1 'i 1 i
L / 11 ' 11_ i.' \ !1
/
/Ii 1 I 1 1 1 / :'n ,I ! I
400
/'-
_,...---/--- .) . 1 I ), Mf .1
M.. M� V \1\.\il '-'\ 0f lj r . I• I"{' \,}.;1,\•
300 200 100 0 •h
>-fl�
'---- -- I I I I I I I L __ J 1 I I 1 I .1 1 [ I I I I I
l'I . I
I I I I I t _ _t_ ,....____.
8.0 7.0 6.0
Fit:u.re IV
5.0 PPM I 6 l 4.0 3.0 2.0
nmr spectrum of Naphthyl Ether IV
(AJcl?ll§:l.-rne thy J naph thy 1 }2�.Y.9:-naph th;/] ether)
22
1 n
"!"OU
-- . -- -- i --j -- - --f- ·- - -[- - .
- - -�-= ��--=; =---- -�.J.--=-�� -=�---: ±_t. 1 I �-��lccJ��!-NJ�J�_l�.T'J-jt=LSk�� _,J� - f • . ' --+<- : .. ' Lhkd ld"'b ,[._J=l:=L . --- -=r=-r-±-···1:.---:�-:- -1-�=�- =·t--= � :_, _ _ f-�-•1=�:+��=.:: -=-r=: --r�--=r--=�T:=1-·-- : - -- ·- - - - 1 ---- 1 -- --- --- -- - - - --- -- --t---- - 1-·-- -- 1 -- . -- __ t__ ----!
--- ·--· - - - ·-- - --- -- --- ----t--- -- ---1 -- -.- ·-- -- -- -- --f-- - I
f - j __
l 01
�r -- +--
801 ! -g�f =1-3�::.FJ.�1'')M"J'l"1C::!�--11•-lt.•l•-.•11 -j/�-�---1 . - '-�180
f
1---- __ , _ __. --- +---t----+ ----- �----1
60�
I ---1 ---
I
20 --:--t-
--"-
. t-I ----+-- . '
I--- • --- . -
i I
--i-1 I
.:: 1�--t:
- -t I --1 -�---0 4000 \35GO 3000
Figure v
2500 2000 FREQUENCY (CM-1)
ir spectrum of Naphthyl Ether I
(Ee t_§_l.-me th.YI naph thyl lig_t.!_l.-naphthyl 2 thf:r)
2J
1500
J� ! 0
..--, .. , , I ---- --- ----- f------- --
! -
i , -
I
: - r ---.--·1 --·1-··-. ' r - · . . . . - r---� - - ; I -• . , . •- . , . 1.. ---y- i l - t • t l· .
1--··- • -i-� -- - ; � - 1 -· -·-
l::-:-:--::.-r_; .!
I I
- . : - _l:Jj__;_ ;:tT: : Fr::, ; · · -i ; - :·r
, .
'.Fl __ _! '. : ; ' t : : : ! ' ; . ' l
1 I
.. ' ; I, I 1 · -·- ... . ·-·--· --· ·- -··-·-·-·· · r·---
r-;-: - · / �� 1 . :, ;· �j�: t i ! l '. i : :-: ; �>;: '
r ____ /_!:---��[� -�--- - -1,1= i;t1- _:=: � � -=I-' =�-,- -�-�-�t-t (J l,
� !
\. � . ..
I I (.I
I 20
i A __ , __ _J_
\ 1-··. . . I �· I . . . .. r, ,� � _ _:_.:_· ._;_j_. � -r -- �--- -f-·: _ _._ , r :_'_ -� - -r-- - :�_!_�-�-- - .i : _ _ ,
I . ' l • • l I I I • I- t 1 I I ' ' I . ! ' I I ' -I I I 1 I ' ' I . l I 1 I I I ---: 1-;-�
-I -- . I
I _' ' -· -'-- --- -- -,--t- 'T �.....:J_ - ·t ... - --
1 ·-- .4 ·1· I I • I ' I ' ' • I - I ' ' . I I I 1- '
· .... ·l· --\ -· ' · 1 l · 1-· · · · 1 • ·r· · · ·
--- •1-l-· --1--r- -... . , � ,_ I I
_'
_'_. -2--r-! - _!� -� _'._� -----�-.::_ I . ��:+� - . ..
L-�1�_,_ -I . . �-; i.j • tj I 1-i ' • , • I j_! I ! I
I �.: �-:- ,. _ 1 : ". . t- .. J: '. -! -- - • i :--! � , -�-�+��. �j·'.· .· �-· _ __ ---- -- · · I I !
\ ' I --I
------ -.. ----+---
l ' _, . ,.. - t I 1--t- I I I I J J • f I - I • ' ' • I I ; .! ·' -f-· ! i · J ---- --·::'._. -;�� -,- ; ·----- 1���,2��- 1• ,_! --1-µ-�--- :--�-P-+:-L -�i--H----; !--· j-r
' -- · , . 1- 1 • I ! I I I ' ' I , I ' I j i : ' I ' - I· ' t . ! I -· I • ' i ' • • j i ; ' : ; : ; : ' .': ' I ' •
I ' ! . L ' : I I_ i ! ___ I,___ ·-r=, . . . -,� ' ·t , , --. 1--;--:;-� , i :--;:::-:- -- _ _,_ :- -. -. : rr;-�-:- -,-1-;-.-.. i - . •. - . ·-:- -� -i- :·-· . ---;-- . : ,. � - : · 1 . : - I ' ! � - '
- t ! - ' ! : j I i I '. ; : . '. ; : � � l I ' . • • ' . . t !__ - • --1 • I I � ' • I j l ' l t ' ' ' ! I I L 1 l ! I !
- --- t--- ,__ �-.. -. ·-·------ � 7�-- :;------1 ! rr-"--T"---:�:r · · 1-r,' :1�·-rrr,, ; ,. ,·: I ";· ! , t ' -- - : . ; : ; 1 - - J " i -r· : � . ; '.: ; �: ; � ; _ __ ;_,_;_ :-�-r- 1' 1 , , • • • , . , • . . . . , .. 1
• , • J -j . . . , 1 ' , 1
.11 I . 1, -·· . • l :�- _:;��:l_F_ .�---!-; i ; - ) -:�-+- -r-���-'-;--,-�-������;� �ti,��-f _:_:·>r----•--:-:: .L ' l i--�- l -l I ' I I I ; ' ' ! • t
ul
!k {
'' ( "'- -
G: · ' . ......
.. �.
-- ·---- j
. -- __ .. __
0
II
- -·-r- : , , J. i-- . -! I l · J , ( . . ! j ! t ; -. ----·- I , :n�-l : : ; -· -- �;1,-: ··- -�·-
I 1--; ·---- --- _:_ - - ·-�f -+-� -- ---·- �-r :- ;::-i---1--�-;-f-- ·---·�- - ' - .. ·-- . - ; ·-+-�-,-:--:--�-:-,.,- ..
i----�-� ··; !-:.:-: -�:::: ·:'; +4+�- ·--·---·-L _____ ·�:.1 __ 1·�,·:11-·--·----l--, • ,
• ; i : : . : ' i ; I ' ' l 1 : [ ' 1 I
, I t , • . • • I···· ' ;:'.ij . I 0 i : ----- -r------- __ .:._ __ __!__�_ J++-r- �-�-:- -·-r+-; -�-H .;._'..-: :- - --·-; -·--·: l' .. ·--·--'-- !-:-'-- -,-:-�--·_J-, - _: - -
I' ·1 · . • ! i I 1 1 · t I • ' I 1 • •
._ ....... ___ ...._ ___ _._ ___ -'------'------'----- - - ---- - -- \ .' 1300 ·1 ��OJ l l 00 1000
Firi�re v
� 00 800 F1' :ouENCY (CM 1)
7' '' r'\ Uv ' , .. ') (Ji,);
-----------· ·-· , --·- ·1
ir spectrum of Naphthyl Ether I
(Bej,_9..-rr.ct�41naphthyJ l?:!�-narhthyl eU1cr)
500 l ,·-.., .•-. "• \)l I
- ' -- · 1
r I 00 ! ·-1-n-+ ! ' ! !
----l---+-
801 I I
[;·
�_,_-1 · 1 r r1-t ' l_�,Gi--ffi�·-rr-. - -f�]-�-lf - i-� :· ��:��-- .� =--��-+==-· -� �-=- ::--� :· - -__ :� = -:--· .:--= :.=::: == -=-- -::::: -��= :=-.: -�� .�---: -=- ���- _:�_-j � _:_ := �_:=--:· - ��-�---- -�:- =-:� .. � =�---- -- --t- -· - - - ,,, - -1 _, - =::- ·· - -.=- - -- -
___ ::=::r __ __ :-.:.:.::_:_ · ::: .. :::- - l - -- --- --=-- .:t -- :. _ __ == :.-_ i :-=: :-=�c===· :·;::c:cc.c;_.=- .c:; - -t ·c1:-::ii0=c0=�:1c -- :·: c=:c=-.. F cc, - -= "; A -·-- r--- - __ __,__ -- -t - ,
-�•••VI ·r
---���· -1 T - ' I. I
I---I , I
r· -_:r-
"""
8(
I; �- -�������������������
���������������������
I i+-
··-� 6( _ _J --
r:. :-:�i=:t� I- ,,
! I l---·
-·-I -�1--i--·-t
' Ir-·. . . /"'--'..,-1 :"' .. r......,:.,.,· -�.--
-'--'--'--
. -- -� ..
�·
2 0 1�· , _ . : --i---:--
n_- � _ -�--+--' 4v
----1-� . -i -- 1-- _ l
- �___________L___
- Lil
-- - ! �-
- -
�---.--L-�--f
1-1---
--�- · I , .
·�-
[ , ' I
-
: I : : - -1- -- 1--· 0 4000 3500 3000
Fi2ure VI
I
I
2500 2000 1500 fREQUENCY (CM·1)
ir spectrum of Naphthyl Ether I I
(Bc.19--mr� thyJ.naphthyl §:1.Pb§:-naphthyl P thcr)
25
4(
21
c
f )
I 0 0 1 I I
... . \ ...
2(J
I
i i
- : . i --·--:--:--;-:Fi--. -:
' ' ' - i------1 -- ---+--· . : ; . : T i . • . · . . . .. I
. . . . . i· -· : - .�L,_ - 1 _: _:_ : - ·--�- ·
! _ : 1-- - -- -:---- ·-·-r-�-; :- -- .-- '. : > I __ : : _
. . . .. I . . ' '-!-· L .:..1. -t ., . I , __ __ .. _; ____ _ r-----1--r
! : - -----·- -·-· r- ·- -. . , I ,
I • •
- ; l ; ; : : ·
· +� :-:-:-I . : � : �/J. : : I . - .
t -:
I . , . 1 1 : ! r ; !
. ... -r-+
-, ·rr-r� -r-i-r;-: I . ! I : i : '
-• ----·· _;--1....:_ I : j ' • - +- j t , . - ' j i ; . !
i ;·· I ' I · ·:-r-1 · ·
, - ; ' •• • · - . . + • r ' - j ; . , . : ! J J : · r ; '. ' . 1,,. 1 . 1
-;--:-: - ;-1-· ' I I
I � ' . �h: ' : ' � ·�! . j i ;�' f /T1�f - � � - 1;- _! .' !T l .
...J_,... ' ...;.....:_ _: __ L_;_C_' � _.;._ --)- ·-·-r 1'·--+- ' - - --: ;_t ; I ' . . ' I I ' ' I I I ' : - • I ' 1 1 ' LW· ' ' . I I ' ' I ' l l I I • I : ' ! i I l I ' I l ; ' i I ' : ' : 1-+_..._,,..........-i-...-+-+-+-!--+...,.,.-+--+-+-.,.._,...... - -- �Ll- --rr--- -- -· - - · · -- . -- · • -
+ ' I·
· i l : i ; ' - i I I l I t . ' I ! . � : � - ! ! l ; l- • ! 1 - i I ' ' ; ·-i-1--��.- j:li- -;r;T t--j fl-T -; -;- -·· · · :· ; . ' , - 1 i 1 i r 1 J 1_1_±_ ; \ 1 ' ! 1
• I I , :-Fr-1 _. _ . . -r· :-:;· rr 1 -• . ' ' I · ·1 . · 1 · · . ' I . I
f \ I . . . . ! ... - . . - ·- ·- ---�--:-r:·· I .
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i_ ; oo 800 700 .soo F 2 Q U E N CY ( CM 1 )
i r s pectrum of Naphthyl Ether I I
(I:. e ta -rn e th y J n aph th y l a lp.ba -naph thy l e the r ) 26
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F i g ure V I I -
FREQUE NCY (CM-1) : 11 spec tr um of .Naph thy l :i: the 1 I I I - -- · •
( A lpha -me thy l naphthyl a lpha -nap h thy l e th e r )
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F . . , QU E N CY (CM 1 )
: i r spe c tr um o f N a ph thyl E the r I I I
( A lpha -me thy lnaph thy l a lpha -naphthyl e the r )
28
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2500 2000 F � EQU ENCY (CM-1)
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F i gure V I I I
;·oo 800 700 " l U E N CY ( C l'/1 1 )
i r spe c tr um o f Naphthyl E the r IV
( A lpha -me thylnaphthyl b e ta -naph thyl e the r )
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F igure IX
3 1 : mas s s p e c tr um of Naph thy l E ther I. ( Be ta -me thyln�phthyl be ta-naphthy l e the r )
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F i g ure X J 2
mas s spectrum of N aph thy l E th e r I I ( B e ta -me thy lnaph thy l §: lpha -naph thyl e the r )
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Figure X I : mass spectrum of Naphthy l E ther I I I ( A lpha -me th y l naphthyl a lpha-naphthy l e the r ) ·
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J4 F i g ure X I I 1 mas s spe c tr um of N aph thy l E th e r IV
( A lpha -me thy lnaph thyl be ta�naphthyl e the r )
m/e
S tandard i z ati on of Naph thjl E the r I and Be ta -naPhth o l U sing
3 ib e n z;yl a s I n -t e rn a l S tand a:!:'d
C ompound Re te ntion C l ; C2 -* A l ; A 2 -�- -�· F 1 ; F2 Time (min . ) ( mg/mL )
Bibenzyl 3 . 2 6 . 6 7 8 0 2 9 0 1 1 0 . 0 8 0 91 7 0
Naphthyl 4 . 1 0 . 2 6 7 43 877 0 . 07 0 8 E the r I 0 . 2 0 0 2 1 3 75 0 . 0 0 1 3
Be ta- 2 . 1 0 . 2 6 7 2 94 7 8 0 . 1 04 Naphth o l 0 . 2 0 0 1 4 1 4 9 0 . 0 0 1 8
S tandardi zati on of Naph thyl E the r I and Be ta-naphthol
Naphthalene as Inte rna l S tandard
C omp o und Re te n ti on · c1 ; c -:i- A1 ; A 2** F1 ; F2 Time ( min . ) ( mg/fnL )
Naphthalene 4 . 6 0 . 5 0 0 1 645 85 1 0 . 3 3 3 7 9 841 0
Be ta- 2 , 7 o . 4 oo 1 1 98 1 1 1 . 146 Naphthol 0 . 5 3 3 1 1 3 8 7 9 - 0 . 034
Naphthyl 14 . 5 o . 4 oo 1 996 08 0 . 6 0 0 E the r I 0 . 5 3 3 2 03 24 0 0 . 0 7 2
* For b ibenzyl and naphthalene , c 1 ; c 2 i s C . l ; C . 2 . l S l S ** F or b ibenzyl and naphthalene , A 1 ; A2 i s A . l ; A . 2 ; l S l S
Integrated areas are ave rage o f d up lic ate runs .
U sing
3 6
S tand ar d i z a t i on of o - Ph e n oxyb e n z o i c A c i d and S a l i c y l i c A c i d
U s i n� Ph tha lic A c i d a s I n t e rna l S tandard .
C ompo u.nd R e tent i on C l ; C 2* Time ( min . ) ( mg/mL )
Phtha l ic 2 . 3 1 . 0 0 A c i d o . 5 7 1
o -Phenoxybe nz oic 7 . 3 1 . 0 1 A c i d 1 . 44
Salicylic 3 . 9 1 . 0 1 Ac i d . 1 . 44
S tandard i zat i on of Na�hthyl E ther I I I ,
U s ing B ibenzyl as Internal
C ompo und Re tenti on
T ime ( min . )
B ibenzyl 3 . 0
Naphthyl 3 . 8 E the r I I I
Alpha - 2 . 1 Naphtho l
S tandard
C 1 ; C 2*
( mg/mL )
6 . 6 7 3 . 33
0 . 53 3 0 . 6 6 7
0 . 5 3 3 0 . 6 6 7
A · A ** 1 ' 2 F 1 ; F2
1 3 95 1 8 1 1 1 8 6 9 1 0
1 35 8 95 1 . 348 24 95 23 - 0 . 2 988
744 2 8 2 . 03 7 1 5 1 934 - 0 . 0 7 25
and Al'pha -na�hthol
A · A * * 1 , 2 F 1 ; F2
1 234 1 9 1 8 745 0 0
5 2 1 4 7 0 . 3 635 85 854 - 0 . 0 05 1
2 8 8 81 0 . 2 1 4 9 4 93 7 2 - 0 . 0 1 0 9
* For phthal i c ac id and biben zy l , c 1 ; c 2 i s c . l ; C . 2 . l S l S
* * F or phthalic ac id and bibenzyl , A1
; A 2 is A . 1 ; A . 2 I n t e gra t e d are a s are average o f d upl i cat e rtlns . 1 s
3 7
S tandardization of o-Anisic Acid and S a licyl i c Ac id U s i ng
Fh thal i c A c i d a s I n te rna l S tan d ar d
Compound
Ph thalic A c i d
o-Anisic Acid
Salicylic Acid
Retention Ti me ( min. )
2 . 7
4 . 2
5 , 6
0 . 6 6 7 7 142 9 0 . 3 3 3 5 855 6
0 . 6 67 455 0 9 0 . 83 3 9023 0
0 . 6 67 2 7 7 6 6 0 . 83 3 6 0554
S tandard i z a t i on of o-Anisic Acid and S a l i cy l i c
Hvdrocinnarilic A c id as In ternal S tandard* *'*
1 0
1 . 6 6 1 - 0 . 05 9
2 . 3 27 0 . 01 0
Acid Usin_g
C ompound Retention C 1 ; C 2* A · A * * 1 ' 2 F1 ; F2 Time ( min . ) ( mg/mL )
Hydrocinnamic 7 . 8 3 . 0 0 7 5 63 0 1 A c i d 2 . 0 0 5 94 04 0
o -Anisic 4 . 1 0 . 5 0 0 741 92 0 . 1 6 93 A c i d 0 . 6 6 7 1 6 1 7 97 0 . 0 0 0 6
Hydrocinnamic 7 . 8 3 . 5 0 3 1 7 8 04 1 Acid 2 . 0 0 1 98 1 1 2 0
S a l i c y l i c 4 . 8 0 . 2 0 0 67 544 0 . 3 0 05 A c i d 0 . 2 8 6 98 6 1 2 - 0 . 0 067
F or phthalic and hydrocinnamic a c i d , c 1 ; c 2 i s c . l ; C . 2 . l S l S
F or ph tha l i c anf :r, yd;: o c i nnam i c a c i d , A 1 ; A 2 i s A . . 1 ; A . 2 l S l S
I nte gra t e d a r e as are av e rage o f d up l i c a te r uns
* * * Th i s c a l i bra t i on wa s d on e at 2 d i f f e r e nt c onc e n tra t i ons
o f the s tandards .
3 8
S tandard i za t i on of P -Ani s i c and P -Hvdr oxvb e nz o i c A c i d U s ing
Comp o und R e t e n t i on
T ime ( miE . ) c 1 ; C * ( mg?mL )
Al ; A2** F l ; F2
H y dr o c i nnam i c 8 . 1 5 ; 45 1 55 946 1 Ac i d 5 , 0 0 7 01 03 0
p -Ani s i c 6 . 1 0 , 0454 1 25 6 97 0 . 0 0 9 A c i d 0 . 0833 1 2 15 7 2 0 . 0 01 1
p -Hydr oxyb e n z o i c 3 . 0 0 . 0454 1 2 063 9 0 . 01 1 7 A c i d 0 , 0833 1 04275 - 0 , 0 007
S tandard i z a t i on of o -E th oxyb e n z o i c A c i d and S a l i cy l i c A c i d . .
U s i ng Ph tha l i c Ac i d a s Internal S (2and ard
C omp ound R e t e n t i o'.':1 C 1 ; C 2* Al ; A 2
* * F1 ; F2 Time ( min . ) ( mg/rnL )
Ph tha l i c 3 . 1 0 . 5 0 0 1 1 85 1 0 1 A c i d 0 . 2 8 6 4 825 8 0
6 -E th oxyb e n z o i c 8 . 7 1 . 1 1 1 944 94 1 . 354 A c i d 1. 27 1 5 82 0 9 - 0 . 0 025
S a l i c y l i c 7 . 1 1 . 0 0 1 2 6 1 07 1 . 7 65 Ac i d 1 . 14 1 05 924 0 . 1 2 1
* F or ph tha l i c �nd h yd r o c i nnam i c ac i d , c 1 ; c2 i s c . l ; C . 2 l S l S
* * F or ph tha l i c and hydr o c i nnami c a c i d , A1 ; A2 i s A . l ; A . 2 l S l S
Inte grate d are a s are ave rage o f d up l i c a t e r uns .
3 9
RES ULTS
Tab le I C l e av i ng agents , s o lve n t , tempe rature , reac ti on time
and e th e r re c ove ry f or naph thyl e th e r r e a c ti ons * *
Exp E th e r N o ,
1 I
2 I
3 I
4 I
5 I
6 I
7 I
8 I
9 I
1 0 I
1 1 I
1 2 I
1 3 I I I
1 4 I
1 5 I
16 I
C leaving Agent
Py • H I
Py • H I
Py · H I
Py • H I
H I gas
5 7% H I
Py . H I F e C 1 2 · 4H 2 0
Py · H I F e S 2
F e S
Py · H I F e S
Li l · 3H 2 o
Py · H I
Py · H I ( Ph ) 2S
Py · H I c oal
c oal
S olvent
Pyr i d i ne
Pyr i d i ne
Pyr i d ine
95% Pyr i d i ne 5% H 2 0
CH 3 CN
Pyr i d ine
aq . H I
Pyr i d i ne
Pyr i d ine
Pyr i d i ne
Pyr i d ine
Pyr i d ine
Pyr i d i ne
Pyr i d i ne
/ Pyr i d ine
Pyr i d i n e
Temp . Time % E th e r ( oc ) ( days ) Re c ove ry
9 0 ° 3 9 6
s5 ° 6 1 03
1 0 0 ° 3 1 01
1 1 0 ° 7 96
7 8 ° 5 94
5 9 ° 3 94
1 3 5 ° 0 . 1 J 6 9*
95 ° 6 95
95 ° 4 9 9
9 0 ° 5 1 0 2
9 0 ° 5 1 02
9 0 ° 5 98
1 1 5 ° 3 1 02
1 1 5 ° 3 94
1 1 5 ° 7 94
1 1 5 ° 7 93
* 0 . 0 2 3 mmo l of be ta -naph th o l wa s al s o d e te c te d ( 13% c l e avage ) .
* * Th e ave rage for e ther re c ove ry i s 96 ± J� .
4 0
Tab le I I : Q uant i tative Analys i s o f Naphthyl E ther Produc t Mixture by HPLC
E xp . E th e r N o .
1 I
2 I
J I
4 I
5 I
6 I
7 I
8 I
9 I
1 0 I
1 1 I ,
1 2 I
Am o unt E ther
( mmo l )
0 , 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
0 . 1 7 6
C le aving Agent
- - - -
Py · H I
Py • H I
Py · H I
Py · H I
H I gas
5 7% HI
Py · H I Fe C 12 · 4H2 0
Py • H I FeS 2
FeS
Py • H I FeS
Li I · JH 2 0
. Amount Area of Area of W t . o f Re c ove red C . A . S tandard · E the r S tandard E the r
( mmol ) ( mg ) ( mmol )
- - - - - 1 3 1 7 07 1 98 575 45 0 0 . 1 6 9 -
0 . 3 0 0 87 07 J 14J 1 2 0 0 0 . 1 8 1
0 . 3 00 5 02 8 8 8 8 941 4 0 0 0 . 1 7 8
0 . 6 0 0 J 646 8 - 1 22 86 8 2 0 0 0 . 1 6 9
0 . 6 0 0 6 01 5 3 987 01 4 0 0 0 . 1 65
J -hr 3 9667 1 3 1 7 1 8 2 0 0 0 . 1 66 b ubb ling
7 , 6 0 1 6645 8 4 0 2 8 07 2 0 0 0 . 1 2 2
0 . 3 0 0 8JJ 82 27 87 93 2 0 0 0 . 1 6 8
O . J O O 57 066 1 98 847 2 0 0 0 . 1 75 0 . 04 0
0 . 0 9 0 1 5 3 2 1 7 24 15 Lr o 45 0 0 . 1 7 9
o . 3 0 0 93 3 1 9 . 1 4 6 95 9 45 0 0 . 1 7 9 0 . 0 9 0
O . J O O 1 27 2 07 1 93 07 1 45 0 0 . 1 7 2
41
Tab le I I Q uanti tative Analys i s o f Naphthyl E ther Prod uc t Mixture by HPLC ( c ont • d )
E xp . E the r Amount C leaving N o . E ther Age nt
( mm o l )
1 3 I I I 0 . 1 7 6 Py • H I
l l1, I 0 . 1 7 6 1f¥11��s 1 5 ' I 0 . 1 7 6 Py . HI
ext . c oal
1 6 I 0 . 1 7 6 ext . c oal
-i� l /5 a l iq u o t was analyz e d
Amount Area of Area of W t . of C . A . S tandard E the r S tandard
( mm ol ) ( mg )
0 . 3 0 0 1 2 62 3 2 1 05 8 2 2 6 0 . Qi�
0 . 3 0 0 1 9 96 1 8 6 01 2 87 5 • Q-!H� 0 . 1 3 0
0 . 3 0 0 1 74 2 7 8 1 1 2 075 2 0 , Q-!Hf- * 0 . 5 0 g
0 . 5 0 g 1 6 1 3 6 0 1 02 8 6 0 2 0 , 0* -lH�
-lH:- 1 /5 a l i qu o t was analy z e d , naph thalene used as inte rnal s tandard
1HH0 1 /5 0 a l iq u o t was analyzed ,
Re c ove r e d E th e r
( mm o l )
0 . 1 7 9
0 . 1 65
0 . 1 65
o. 1 63
4 2
Tab le I I I C le aving agents , s o lvent , tempe rature , reac ti on
time and e ther re c ove ry f or c leavage re ac ti ons
inv o lv i ng o -anis i c ac id and re late d e thers * *
Exp E ther C le aving S olvent Time Temp % E the r % C lvg* N o . Age nt ( days ) ( oc ) Re c overy Prod uc t
A q -anis i 6 ; acid Py · H I Pyridine 3 85 ° 8 0 1 0
B o -anis i c - ac i d Py · H I Pyridine 3 1 1 5 ° 1 0 8 6
c o -ani s i c ac i d Py . H I Pyridine 3 1 1 5 ° 1 8 7 6
D o -ani s i c ac id K I Pyridine 3 1 1 5 ° 3 3 5 8
E o -ani s i c a c i d Li I · 3H2 0 Pyridine 3 8 5 ° 44 54
F o -anis ic ac i d Py · H I CH3 CN 4 75 ° 9 9
G o -anis i c ac i d K I in 1 8 - CH3 CN 4 7 5 ° 94 c -6 e th e r
H o -ani s i c ac i d Py · H I DMS O 4 7 5 ° 94
I o - e th oxy - Py · H I Pyridine 3 1 1 5 ° 84 1 8 be nz oic ac i d
J p-ani s i c .ac id Py • H I Pyridine 3 1 1 5 ° 96
K o -phe noxy- Li I · .3H 2 0 Pyridine 5 9 0 ° 94 benz oic ac id
L o -phenoxy- Py · H I Pyrid ine 3 1 1 5 ° 1 01 benz o i c ac id
I * The c le avage prod uc t de te c te d was sali cyli c ac id .
-i"* The ave rage f or mass : · bji.lNce:::;> is 96 .± 37; .
4J
Tab l e I V Q ua n t i tat ive Ana lys i s of o -Ani s i c A c i d an d R e la te d E the r R e a c t i ons b y HPLC
E x p . N o .
E th e r
A o -an i s i c ac i d
B o -an i s i c a c i d
C o -an i s i c a c id
D o :... an i s i c ac i d E o -an i s i c ac i d
F o -an i s i c ac i d
· c o -an i s i c ac id
H o - a n i s i c ac i d I o - e th oxy
b e n z o i c ac i d J p -an i s i c ac i d
Am o un t E th e r
( mm o l )
0 . 1 75
0 . 1 75
0 . 1 75
0 . 1 73
0 . 1 75
0 . 1 75
0 . 1 75
0 . 1 75
0 . 1 6 2
0 . 1 7 9
K o - phe n ox y b e n z o i c 0. 1 75 ac i d
L o - ph e n oxybe n z o i c 0 1 75 ac i d
C l e av i ng Age nt
Py · H I
Py · H I
Py . H I
Am o un t C . A .
( mm o l )
O . J J J
O . J 1 0
O . J O O
K I O . J J J
Li I · JH2 0 O . J 7 0
Py • H I O . J O O
KI in 1 8 - O . J O O c -6 e the r 0 . 0 6 0
Py . H I
Py • H I
Py • H I
O . J O O
O . J O O
O . J O O
Li I · JH2 0 O . J O O
Py • H I 0 . J O O
* The i nte rnal s tandard was ph tha l i c a c i d ,
-1H< 1 /5 a l i q u o t was ana l y z e d .
Are a of Are a o f S tandard E th e r
2 7 91 7 2
25 885 8
25 6JJ 6
2 64846
1 85 9J 6
1 J45 J 2
1 2 03 86
1 J 7 035
6 2 3 04
3 2 8 846
1 0 2 9 74
1544 97
2 1 8 0 8 0
2444 8
4J 1 0 7
8J 1 4 7
4J 6 6 2
1 1 1 5 08
942 14
1 08246
2 0 84 8 8
2 7 891 0
1 4 9 8 0 0
2 02 0 2 0
W t . o f * * * S tandard ( mg )
3 2 • Q-IH�
J 2 • Q-IH
3 2 ' Q-IH�
J 2 . 0* *
J O O . O
2 0 . Q-1< 2 0 . 0-1<
2 0 . 0-1< * 1 , Q-IH<
J O O . 0* * * -1� 2 0 . Q-1<
5 . Q�-1<
E the r R e c ov e re d ( mm o l )
0 . 1 4 0
0 . 0 1 7
O . OJ 2
0 . 05 7
0 . 0 77
0 . 1 74
0 . 1 64
0 . 1 65
0 . 1 3 6
0 . 1 7 2
0 . 1 6_5
0 . 1 7 6
* * * U n l e s s s p e c i f i e d o th e rw i s e , th e inte rna l s tandard u s e d was hydr o c innam i c a c i d .
* * * * 1 /1 0 a l i q u o t wa s ana ly z e d .
44
D I S CUS S I ON
The ana ly t i c a l pr o c e d ur e f or the HPLC q uan t i ta t ive ana ly -
s i s was d one i n th e f o l l owing way : A me th od c a l le d 2 -p o i n t
c a l ibrat i on wa s u s e d . D up l i c a t e d e t e rmina t i on of tw o s o l u t -
i on s c onta i n i ng d i f f e r e n t c onc e ntra t i or.s of s tandard c omp o und s
and inte rna l s tandard w e r e i n j e c te d into the HPLC . S inc e the
2 s o l ut i ons c on ta i n known am o un t s of e ac h c omp one nt and the
a r e a s und e r th e p e ak s are int e gra t e d , a r e s p on s e fac t or c an
b e c a l c ula t e d ·. I n c a l ibra t ing aga ins t an inte rna l s tandard ,
a p l o t o f the c,on c e ntra t i on o f s ample/c onc e n tra t i on o f inte rna l
s tandard v s . are a of s�mp le/area of inte rnal s tandard w o ul d
y i e ld th e s l op e (�Y/�X ) calle d F1 and t h e Y - i n te rc e p t ( Y 0 )
called F 2 .
C one . of sample C one . of int e rna l s td .
I <l y I I
Area of sample A r e a o f inte rna l s t d .
c� x c . 1 - cA x c . z F � 1 8 • l S
1 = C . 1 x C . 2 ( A�/A . 2 - A4/A1. 8i) 1 8 1 8 4 1 8 .£,;
c 1 c onc e ntra t i on of s tan dard s amp l e 1
c 2 c onc e n tra t ion of s tandard s amp l e 2 c . 1 1 8 c onc e ntra t i on o f i nt e rnal s tandard
c . l S 2 c onc e ntra t i on o f inte rna l s tandard
Al p e ak are a of s tandard s amp l e 1
A2 p e ak are a of s tand ard s amp le 2 A . l S 1 p e ak are a of i n t e rna l s tandard in
A . 2 p e ak are a l S of i n t e rna l s tandard in
C 2 F A2 -- - 1 x --c . 2 A . 2 1 8 l S
i n s tandard sample
in s tandard s amp l e
s tandard s amp l e 1
s tandard s amp l e 2
W i th the re s p ons e f a c t or f or th e c omp o und o f in t e r e s t
d e t e rm i ne d , i f a kn own am o unt o f inte rna l s tandard j s n ow
a d d e d t o a r e a c t i on mix ture , th e c onte nt of the m i x ture c an
b e c a l c u l a t e d :
ws p
l = ( Fl . x A . /A . + F2 . ) x w . l l l S l l S
Wh e r e :
A . = are a of s amp l e l
A i s = ar e a o f i nt e rna l s tand ard
Fl . = re s p ons e l fac t or f or s l ope
F2 . = r e s p ons e l fac t or f or j n t e r c e p t
W i s = we i gh t o f i n t e rna l s tandard
w = we i gh t of ma t e r i a l i n th e s amp l e s p l
I t s h o 11l.d b e n o t e d tha t th e ab s o l u. t e we i gh t of th e
m a t e r j a l in �h e s amp J e can be c a l c u la t e d d i r e c t ly e ven th o ugh
1
2
4 6
the calibrat i on was d one in te rms of c onc e ntrati on be cause
b o th the c ompound of inte re s t and the in te r�a l s tandard we re
in the same volume of re ac ti on mixture and th u s the fac t or
f or v olume c ance l.S out in the c omputati on .
Attempte d C le avage of Naphthyl E thers I and I I I with Pyridine
Hydri odide and Other Cleaving Agents
Reac t i ons of naphthyl e thers were c onduc te d to unders tand
the re s ults of Mayo e t a11 0 who had sh own that pyridine hydr
i od ide in pyridine at room temperature d e c re ased . . the mole c ular
we ight and inc rease.cl the pheno lic - OH c ontent of an I llinoi s
N o . 6 asphalt o l frac ti on . Pyrid ine hydri od ide in pyridine at
5 0 ° reduc e d the mole c ular we ight of an I llinoi s N o . 6 asphaltol
frac ti on t o the same exte nt as s od i um in liqui d ammonia . In
b oth c as e s it i s be lieved that the e ther l i nkage s in c oal are
be ing c le ave d .
Experiment N o . 1 s e rve d as a c ontrol e xperirr.e nt whe re no
c le aving age nt was adde d . W i th e the r I in pyr i d i ne f or 5 days
at 9 0 ° , re c ove re d e ther after work-up was 96% .
In e xperiment 2 , e ther I was reac te d wi th pyridine hydr
i od ide in pyrid ine at 85 ° f or 6 days , I n experiment J , the
temperature was rai s e d t o 1 0 0 ° but the re ac t i on t ime shorte ne d
t o 3 days . N o e ther c le avage was de te c te d i n b o th runs , e the r
re c ove ry be ing 1 03 % --and 1 01% re s pe c t ive ly .
In e xperiment 4 and 5 , c le avage wi th pyr i d ine hydri od i de
was attemp te d in o the r s o lve nts s uch as 95 ;:; pyr i d i ne /5% water
o r ac e toni tri le . In the se s o lvents , no c le avage pr oduc ts were
47 f o und and e ther re c ove ri e s we re 96% and 94% re spe c tive ly .
In e xperime nt 6 , H I gas was b l e d into a pyrid ine s o lut-
i on of e ther I f or 3 hours , then the reac ti on was allowed to
proc e e d at 5 9° f or 3 days . E ther re c ove ry was 94% ,
Hydroi od i c ac id i s known as a s tandard c leaving agent of
alkyl e th e rf 0 . In exper iment 7 , aque ous H I i s te s te d in c le av
ing e the r I , the reac ti on was c arr i e d o u t at 1 35 ° f or 3 hours ,
e ther re c ove re d was 6 9% and 1 3% be ta-naphth o l was de te c te d .
Th i s run sh owed e ther I undergoe s c le avage und e r s tandard
e ther c le aving c onditi on&.
I t i s rep orted that I llino i s N o . 6 c oal c ontains about 2 1 0 . 9% Fe . Exper iment 8 was d one t o f ind out if the iron pre -
s e nt in c oa l may aid pyrid ine hydr i odide in c leaving e ther
l i nkage s . Ether I w a o reac te d wi th Py · H I and Fe C 12 . 4H 2 o in
pyri d ine a t 95 ° f or 6 days , re c overe d e ther was 95% and no
c le avage prod uct d e te c te d . S ulfur i s anoth e r e lement pre s ent
in s igni f i c ant amounts in c oal , a typical I llino i s N o . 6 c oal
c onta ins ab out J . 5% s 2 1 . FeS 2 was te s te d as a p os s ible cat
a lys t for e ther c le avage wi th Py · H I . FeS 2 wi th Py · H I was reac t
e d wi th e ther I in pyridine at 95 ° f or 4 days i n run 9 , no e ther
c le avage was obs e rve d and e ther re c ove ry was 99% . 2 2 Kamiya e t al reporte d that c oa l a s h , s pe c ifi c ally s i li c a -
alumina and i r on s ulfide , /e nhanc e s the d e c ompc s i ti on o f mode l
e th e r s at 4 o o 0 . E�pQ rime n t 1 0 was d one t o che c k if iron s u l-
f i d e maybe ac t ing as an e ther c le aving agent . N o c l e avage was
obs e rved wh e n thi s reage nt was reac t e d w i th e ther I a t 90 ° f or
5 days and e th e r re c ove ry wa s 1 02% . I n experime nt 1 1 , its
poss ible func t i on in a j d i ng Py · H I in e ther c leavage was als o
48
te s te d . Whe n e ther I was reac ted w i th Py ' H I and FeS in pyrid
ine at 9 0° f or 5 days , no c le avage re s ulted and e the r re c overy
was 1 02% .
In e xperiment 1 2 , Li I · 3H2 o wa s used as a c leaving agent .
Li th i um i od ide c le aved 2 -me th oxynaphthalene in c ollidine at
1 7 2 ° 23 . A t 9 0 ° f or 5 days in pyrid ine h oweve r , e ther I d oe s
not undergo c le avage wi th thi s reagent , e ther re c overy be in g
98% . In e xper iment 1 3 , naphthyl e ther I I I was s ub j e c ted t o
c le avage reac t i on wi th pyridine hydri odide in pyridine at 1 1 5 °
f or 3 day s . N o c le avage was obs e rved and re c overy was 1 02% .
In experiment 1 4 , phenyl s ulfide was te s te d f or i ts catalytic
ac tivi ty with Py • H I i n c le aving e ther I . The reac ti on was run
in pyridine a t 1 1 5 ° f or 3 days , no c le avage was observed and
e ther re c ove ry was 94% .
The s e reacti ons are interpre ted t o mean the general inert
ne s s of benzylic naphthyl e thers t o mi ld c le aving agents s uch
as Py . H I . I t sh ould be recalle d that Py • H I in pyrid ine at
r o om temperat ure d e c re as e s the mole c ular we ight and increases
the phenolic - OH c ontent of an asphaltol fracti on , h oweve r ,
th i s same re agent in pyrid ine d o e s not c le ave benzylic naph
thyl e thers at 1 15 ° , therefore , one can safe ly c onc lude that
the se s imple e th e r linkage s are not re spons ible for the change s
obs e rved by Mayo e t a1 1 0 .
The e nvir onme nt ins ide the c oa l matrix may be c ond uc ive
f or e ther c le avage . In e xpe rime n t 1 5 and 1 6 , the e ffe c t of '
c oal on e th e r c le avage reac ti ons we re te s te d , In expe rime nt
1 6 , extrac te d c oa1 1 6 ( pyrid ine ins oluble frac ti on ) was reac ted
w i th e ther I i n pyrid ine a t 1 1 5 ° f or 7 days , no c leavage was
ob s e rve d and e th e r r e c ove ry wa s 93% . In e xp e r im e nt 1 5 , e th e r I
wa s r e a c t e d w i th Py · H I and e x tra c te d c oa l a t 1 15° f or 7 days ,
n o c l e avage r e s u l t e d and e th e r re c ove r e d was 94% . Th e r e are
s e ve ra l th ings t o me n t i on ab ou t th i s ob s e rve d re s u l t of e th e r
r e a c t i on of Py . H I i n c oa l . F i r s t , the re i s a lways th e p o s s i -
b i l i ty tha t e th e r I and Py ' H I we re n o t drawn i n s i d e th e c oa l
ma t r i x e v e n af t e r r e p e a t e d ly we t t ing the c oa l wi th the e th e r
s o l u t i on , h e n c e t h e r e a c t i on d i dn ' t re a l ly o c c ur ins i d e the
c oa l . S e c ond , onc e e th e r I ge t s i ns i d e th e c oa l matrix , i t
may i n t e r c a la t e w i th in the c oa l s truc t u r e and th u s r e nd e r i n g
c l e avage r e a c t i o n wi th Py • H I e ve n hard e r t o o c c ur . Th ird ,
Py . H I d o e s n o t c le ave e th e r I e v e n i ns i d e th e c oa l ma trix .
C le ava2_ e R e a c t i ons of o -Ani s i c A c i d and R e l a t�_sLA c i d s wi th
Pyr i d i ne H yd r i o d i d e and O the r C le av i n��p t s
The s tandard i za t i on o f o -an i s i c a c i d and s a l i c y l i c ac i d
aga i ns t hydr o c i nnam i c a c i d w a s d one twi c e . I t wa s ob s e rve d
tha t the f ir s t c a l i bra t i on was m ore a c r nra t e in q uan t i ta t i ng
o -an i s i c a c i d r e c ove ry wh i le the s e c ond c a l i b ra t i on was m or e
s e ns i t ive t o s a l i c y l i c ac i d . Th u s , a c omb ina t i on of the 2
c a l i bra t i ons was u s e d . A ls o , i t i s hard to ge t r i d o f th e
las t tra c e s o f pyr i d ine e v e n a f t e r the w o rk - up , wh i c h.
sh owe d
up a s a sma l l p e ak a t o r ne ar the i n t e rna l s tandard p e ak .
H e n c e , a c or r e c t i on o f the i n t e rna l s tandard p e ak has be �
d one t o c or r e c t f or the pyr i d i ne 1 1ac kgr o und . 'I'y p i c a lly , the
i n te rna l s tand ard h a s an area of J 0 0 , 0 0 0 un i ts whi l e the
pyri d i n e p e 2 k re £" i s t e r s ci.n ::n · f a o f J O , 0 0 0 L:ni t s . ,_, .
50
A l i t e ra ture s e ar c h on c l e ava ge r e a c t i o n s o f o -a�i s i c ac i d
and r e la t e d a c i d s wa s c ond uc t e d , �IJ R oy e r .U tlc:. .- s h ow e d tha t
p -an i s j c ac i d i s c J e av e d b y pyridine hydrochloride a t 22 0° to
p -hydr oxy b e n z o i c a c i d i n 7 0% yi e ld . Mc Carthy e t a 1 2 5 r e por t e d
that NaCN in D MSO c le ave s the f o l l owing :
C ompound Prod uc t Time TemJ� Yie ld -�-- - --( hrs-:- ) ( O C ) (% )
2 -me thoxynaphthal e ne 2 -naphth ol 24 1 8 0 7 7
1 -me th oxynaph thalene 1 -naphthol c:. 1 8 0 7 7 _,
o -ani s ic acid salicylic ac id 8 1 8 0 8 9
2 6 2 7 . Mc Omie and Pre s s ' rep orte d that b oron tribromide c le ave s
the s e following e thers a t room tempe rature :
C ompound Produc t Yi e ld ( % )
1 -me thoxynaphthalene 1 -naph tho l 14
2 -me thoxynaphthalene 2 -naphthol 6 7
o -anis i c ac i d sali c ylic ac id 94
p -anis i c ' ac i d p -hydroxybenz o i c ac i d 92
p -e thoxybenz o i c ac id p -hydroxyben z oi c ac id 94
A s ye t , n o e the r c l e avage w i th pyr i d �ne hydri odi de has
b e e n r e p or te d . A l s o , the re s ult s of e ther c l e avag e w i th p yr i d
i ne h ydr i o d i d e i n pyr i d ine w i l l he lp u s ga i n a b e t t e i under-
s tand ing o f M a y o ' s w o r k o n c oa l w i th p yr i d ine h yd r i o d i d e .
I n e x pe r im e n t A , o -ani s i c a c i d wa s r e a c te d w i th pyr i d ine
h yd r i c d i d e i n pyr i d i ne at 85 ° f or 3 days , 10% s a � i c y l i c ac i d
5 1
was d e te c te d and 8 0% e th e r · was re c ov e red . In e xp e r ime n t s E
and C , o - ani s i c ac id was r e a c te d w i th pyr i d ine hydri o d i d e in
p yr i d ine at 1 15 ° f or 3 days , ave rage of the 2 r uns showe d 8 1%
c le avage and 14% e ther re c ove ry .
R e a c ting KI with o -an i s i c a c i d in pyr i d i n e at 1 15 ° f or
3 days in e xp e r ime nt D , re s ul te d in 5 8% c le avage and 3 3% re c -
ove re d e the r . Li th i um i od i d e i s known t o c le ave 2 -me thoxy -
naph tha l e ne in c ollidine at 1 7 2 ° 23 Thi s re agent was te s te d
i n c le aving o -ani s i c ac id i n pyrid ine a t 85 ° f or 3 days in
e xp e r ime nt E , 54% c le avage and 44% re c overy was obs e rve d .
In e xperiment F , o -ani s ic ac i d was reac te d wi th Py · H I in ace to
ni tri le f or 4 days a t 75 ° , no c le avage was obs e rve d and re c ov
e ry of o -ani s i c ac id was 99'fa . In expe r iment G , o -anis i c ac id
was reac te d wi th KI and 1 8 -c r own-6 e the r in CH3
CN at 7 5 ° f or
4 day s , n o c le avage re s ulte d and e ther re c overe d was 94% .
In e xperiment H , o -ani s i c ac id was rea c t e d w i th Py . HI in DMS O
a t 75 ° f or 4 day s , e ther re c overy was 94% and no c le avage was
obs e rve d . In expe riment I , o -e th oxybe nz o i c ac i d was reac ted
wi th pyrid ine hydr i od i de in pyr i d ine a t 1 1 5 ° f or 3 days , 1 8%
c le avage was obs e rve d and e ther re c overe d was 84% . In exper
iment J , p -anisi c ac i d was re ac te d with Py • HI in pyridine at
1 1 5 ° f or 3 day s , no c leavage re s ulte d and p - ani s i c ac id re c ov
e re d was 96% .
In e xp e r ime nt K and J , o �phe n oxyb e n z o i c a c i d was te s t e d
f or c le avage w i th li thi um i od i d e o r Py . H I . Wi th Li l ·)H 2 o in
pyr i d i ne at 9 0 ° for 5 days , no c le avage occurred and 94% e the r
was r e c ove re d . In pyr idine w i th Py . H I a t 1 1 5 ° f or 3 days , 1 01%
e ther was re c overed and no c leavage was ot s e rve d ,
Bas e d o� the s e re sults , the f o l l ow img are n o te d :
o -Ani s i c ac id und e rgoe s more exte ns ive c leavage ( 81% ) than
o -e thoxybe nz o i c a c i d ( 1 8% ) wi th Py . H I und e r s imi lar c ondi ti or.s ,
wh i le o -pEe n oxyben z o i c a c i d i s not c le ave d at all . Thi s i s
s ugge s tive of a n SN2 me chani sm : the e thyl group i s re lative ly
hind e re d c ompare d · t o the me thy l group f or a backs ide attac k
by an i odide i cn . S tre i twie s e r2 9 re p orte d that the me thyl
group undergoe s SN2 re ac t i on fas t e r than the ethyl group by
a re lative rate of J O : 1 in s imple sys tems . The phenyl group
d oe s not undergo SN2 reac ti on , hence the ine r tne s s of o-phenoxy
benz o i c a c i d t o • Py · H I .
Can interna l pro t onati ori of the e ther oxygen of o -ani s i c
ac id occur ? W i l l i od ide i on be e qually , e ffe c tive i n c le aving
e the r A as we l l as e ther B ?
0 i i ©eol,
...... . ·· 0 " c H 3
A B
K ovi e t alJ O mea s ured the s uc c e s s ive pKas of sali cylic acid
on going from c oncentrate d ac i d t o c onc e n trated base s o luti ons ,
b o th in the ground and exc i te d s tate s :
rArC�� H l8-lok
][
5 3
The y c on c lud e d that the pa th g o ing from I � I I � I I I �vr occurs
in the gr o und s tate whi le the path fr om I - Iv - V -"'> V I o c c ur s
i n the exc i te d s tate .
v I I I
A the ore ti cal c alc ulati on of the ta u t ome r ism of V � I I I
(s i n c e both d on ' t c o-e xis t in the gr o und state ) ba s e d on the
given pKas showe d I I I as the pre d omi nant t a u t o�e r , w ith a
re la tive pKa = - 6 . 5 , or J . 2 x 1 06 ta utome r i c form I I I p e r
m o l e c u l e o f V . In c ons i d e ra t i on of thi s the ore t i c a l basi s ,
thi s type of i nte rnal pr o tonati on appe a r s l i ke l y in the gr o und
sta t e :
D
On the o ther hand , Paul and S chulman2 8 ob s e rv e d that n o
s uch intramole c ular or inte rmole c ular ph o t o tautome ri sm o c c urs
with p -hydroxyben z o i c ac id .
of p -hydroxybe·nz o i c
© HO, ,,,_ o H c "
c¢J 0 Ii
- H +-� �
pkq = - 7. (,
ac i d in
O H
The y measure d the s uc c e s s ive pKas
the gr ound s ta te :
0 0 0 o , " c-::;::- ti c..� o
- H + © f�3© � �
fKa " 4 .s Of-\ oe
o-Ani s i c ac i d may be more s us c e ptible to SN2 - type displace
ment by an i odide i on . Whe the r in the tautomer C ( where the
me th oxy group is hydrogen bonde d by the carb oxyli c hydroge n )
o r i n the tautomer D ( where intram o le c ular hydr ogen transfer . .
t o ok pla c e ) , the e the ric oxygen i s rendere d e le c tropos i tive
and thereby fac i l i tating an SN2 attack by the i od ide i on .
0 @�.,,o h :; - . � . · �
_ .· - C l\ �l 0 "
�-t J' C k'l A:/ � I.-
N o intramo le c ular hydr oge n b onding i s po s s ib l e in p-ani s i c
a c i d , henc e an S N 2 a t tack is n o t fac i l i ta te d . I n view of
55
the s e arg ume n t s , it i s appare n t wh y o -ani s i c ac i d is c le av e d
b y P y · H l b ut p -ani s i c a c i d i s n o t .
Why d oe s the re ac t i on oc c ur only in pyrid ine and not in
ac e t on i tri le or d ime thyl s ulf ox id e ?
The re are seve ra l pos s ible explanati ons : B o s and Dahmen3 1
reported that whi le benz oic ac id has a pKa = 4 , 0 in wate r at
25 ° , it has a pK = 1 1 in pyrid ine , wh i c h me ans that normally a weak ac ids are even we ake r in pyr i d ine . o -Ani s i c a c i d , wi th
pKa = 4 , 2 in wat e r at 25 ° , i s e s tima te d t o show a pKa .-v 1 1
in pyridine , In othe r words , the carb oxyl hydrogen of o-ani s i c
ac i d i s not transferre d i n pyridine and thus c an par t i c ipate
in hydrogen b ond ing with the me thoxy group .
A more s ub s tantial argument would be to find the e qu i l ibri um
c ons tant of thi s reac t i on :
+
0 1 1 c--� K ei
J.I __ \ : r---6 ' c " 3
Thi s expre s s i on can be broken d own into 2 e quat i ons , the val ue s
of which are re ad i ly avai lab le in li te rat ure 3 Z , 3 3 .
__ \ � +
K, = 1 . 6 x 1 0 - 9 D
The e qui l ibruim c ons tant of th i s re ac ti on in water at
25 ° can thus be calc ulate d , The c a lc ulated Ke q howeve r , i s
f or e q ui libruim oc c uring i n water s oluti on and hence i ts
val ue may be t o o sma l l f or the ac tua l Ke q in pyrid ine , henc e
the value i s to be taken only as a r ough e s timation of the
ac tual K , e q
+ �© �t.J-1-\ +
The smallne s s of the value of Ke q s ugge s t that intermole c ular
pro t on transf e r be twe e n o -ani s i c ac id and pyri d ine d oe s not
take s plac e to any appre c iable extent in water at 25 ° , Which
means that in the pre sence of pyridine , the c arb oxyli c hydrogen
of o -ani s i c ac i d i s available f or inte rnal hydrogen bonding
or protonati on w i th the ad jacent me th oxy gro up .
Ware �t a 134 , in the ir work wi th hydroxynaphtho i c ac id
and pyridine , be l i eve d that pyrid ine f orms a c omplex wi th the
ac id ic pro t on of the c arb oxyl group :
0
��/oH �c· ....... i t
+
0 II 0 ( ........ ........ i-1 - · • • • Py
In the proce s s , -pyri-dine might be we akening the carb oxyl 0 - H
b ond , ac ting as pro t on transfer agent and fac i li tating intra
mole c ular hydr ogen trans fer . Thi s e ffe c t i s abs e nt in e i ther
DW.S O or ac e toni tr i le be cau se ne i the r of the s e 2 s olvents i s
5 7
inv o lve d in c omplex f ormati on .
I t i s known that c arb oxylic acids d imeri z e in s oluti ons35 .
� o .Q R- c
' O - H
�0 . . - · · · H - o , R- c c - R
\ I; 0 - H - · · · - o ·
Be cause of th i s d ime r i z a t i on , the re i s c ompe tition f or the
carb oxyl hydroge n ava i lable f or internal hydr ogen bonding or
internal pro t onati on of the ad j ace nt me thoxy group , henc e .the
numbe r of m o le c ule s pre s e nt as interna lly hydrogen b onde d
f orm i s dimini she d . B ut if pyridine i s avai lable t o c omplex
the carb oxyl hydrogen , d imeri zat i on is re d uc e d and most of the
o -ani s ic ac id i s pre s e nt in the reac tive f orm , i . e . ,
wi th thi s c omplex avai lab le , c leavage reac t i on may be more
fac i le .
In the order of increas ing c le avage reac t i on , the follow-
ing s e ri e s i n pyrid ine was obs e rve d :
KI < Py · H I ( LiI · JH2 o
The capac i ty of KI as a c leaving agent i s limit e d by i ts s ol
ub i l i ty in pyr i d ine . Whe reas li thi um i odide i s c omple te ly
s olub le in pyridine at 85 °, KI i s not c omp l e te ly s oluble in
pyrid ine e�e n at-1 i5 ° .
May o .e.±. ai1 0 rep orted that pyridine hydri od ide de creas ed
the mole c ular we ight and inc reas e d the phenolic - OH c on tent
of an I l lin o i s c oa l frac t i on at r o orr. tempe rature . Furthe rmore ,
5 8
they reported tha t l i th i um i odide i s e q ually e ffe c tive as
pyridine hydr i odide in reproduc ing the ab ove re s ults wi th
the c oal frac t i o� .
Naphthyl e thers , spe c ifically beta-me thylnaphthyl be ta
naphthyl e ther and alpha -me thylnaphthyl alpha-naph thyl e the r ,
¥hen .reac te d wi th e i the r Py • H I or· Li I · 3H2 o in pyridine at 1 15 °
f or 3 days , no c le avage was de te c te d and quanti tative re c overie s
of the s tarting e thers we re obtaine d . On the o the r hand , when
o -ani s i c ac i d and o - e thoxybenz o i c ac id was reac ted with Py • H I
in pyrid ine a t 1 15 ° f or 3 days , 8 1% and 1 8% c le avage was obs
e rve d re spe c t ive ly . o -Ani s i c ac id wi th Li I · 3H2 o in pyridine
a t 85 ° f or 3 days re s u l t e d in 54% c le avage .
Th 1 . . t 1 4
. . b e s e re s u t s are c ons is tent wi h Lars e n ' s M o s s aue r
s tudy o f the t i n derivative o f I llinois N o . 6 C oal . He c onc lud
e d that almos t a l l o f the - OH i n I llino i s N o . 6 C oa l may· be in
hydrogen b ond e d f orm . F or o-ani s i c ac id and o -e thoxybenz oic
ac id , the firs t s te p in e ther c le avage , that i s , pro t onat i on
of the e ther oxygen , d oe s not require an external pro t on s ourc e
be caus e the ir e theric oxygens are already in hydrogen b onde d
f orm . F or the s e c ompounds , attack by an i odide i on on the
a lky l group i s s uff ic ie nt to c le ave the s e e thers , In d ire c t
c ontras t , p-an i s ic ac id , in whi c h no s uc h in tramole c ular
hydrogen b ond ing i s p o s s ible , showe d no c le avage with Py · HI
in pyrid ine at 1 1 5 ° f or 3 days .
The s e re s ul ts ind icate tha t e thers linke d t o aromati c r ings
whe re the ortho ring s ubs t i tuents are capab le of hydrogen . b ond
ing wi th the s e e thers maybe be t te r mode ls than e thers linked
t o monosub s t i tute d ring s ys tems f or th ose l inkage s pre sent in
c oal .
Re ferenc e s :
1 . Rubert o , R . G . , Cr onaner , D . C . , Jewe l l , D . M . and S e s h a d r i ,
K . S . , F u e 1 , 1 97 7 , 2..£ , 2 5 •
... 2 . Take gami , Y . , Ka j iyama , S . , and Yokokawa , C . , F ue l , 1 963 ,
42 ' 2 91 .
3 . Wach owaska , H . and Pawlak , W . , Ft.:.e l , 1 97 7 , 2..£ , 4 2 2 .
4 . Lars e n , J . W . , E d . , " Organi c Chemi s try of C oal " , ACS
Symp os i um S e ri e s , Washington , D . C . , 1 97 8 , p 1 2 6 .
5 . Berk owi t z , N . , "An I ntroduc t i on t o C oa l Te chnology " , Acad -
emic Pre s s Inc . , New Y ork , 1 97 9 , p 1 15 .
6 , Takemura , Y . , I t oh , H . and Ouchi , K . , Fue l , 1 981 , 6 0 , 3 7 9 .
7 , M obley , D . P . and Be ll , A . T . , F ue l , 1 97 9 , j§_ , 6 6 1 .
8 . Wach ows ka , H . , Nand i , B . N . and M ontgome ry , D . S . , F ue l ,
1 974 , .u.. 2 1 2 .
9 . Igna s iak , B . S . and Gawlak , M . , Fue l , 1 97 7 , 2..£ , 2 1 6 .
1 0 . May o , F . R . , Buchanan , D . H . , and Pave lka , L . A . , ACS D iv .
Fue l Pre prints , 1 98 0 , .£2 ( 2 ) , 1 82 .
1 1 . Odinokov , S . E . , Mashkovsky , A . A . and G la z unov , V . P . ,
S pe c trochimi ca A c ta , 1 97 6 , 3 2A , 1 355 .
1 2 . R oye r , R . , B uis s on , J , P . and D e rmerseman , P . , Bull . S oc .
Ch im . Fr . , 1 97 1 , 8 , 43 62 .
1 3 . Che n , M . Y . , "Pyridine Hydrogen I odide as an E ther Cleav
ing Age nt in C oal Chem i s try " , M . S . Th e s i s , E a s t e rn I ll i
n o i s Univers i ty , 1 98 1 , p 23 .
14 . Lars e n , J , W . , Nadar , P . A . , M ohamma d i , M . and M ontan o ,
P • A . , F u e 1 , 1 9 8 2 '· 6 1 , 8 8 9 •
1 5 , C o ok , O . , Can . J . Chem . , 1 96 1 , .12. , 2 0 0 9 .
1 6 . B a l lard , IVJ , L . , " Ana lys i s o f C oa l Frac t i ons U s i ng D i br om o -
tr i ph e ny lph o s ph orane " , M . S . Th e s i s , E a s t e rn I lli r" o i s Uni v s r -
s i ty , 1 98 1 , p 5 9 ,
1 7 . Chapman , N . B . and W i l liams , J . F . A . , J , Am . Chem . S oc . ,
1 9 5 2 ' 2± , 5 04 5 •
1 8 . King , F . E . and Henshe l l , T . , J . Chem . S oc . , 1 945 , 4 1 7 .
1 9 . D ' I nc an , E . and Vi out , P . , Te trahe dr on , 1 975 , J1. , 1 5 9 ,
2 0 . Voge l , A . I . , " Prac t i cal Organic Chemi s try " , Lowe and
·Bryd one Ltd . , Lond on , 1 95 6 , p J l 6 .
2 1 . Karr , C l�renc e Jr . , E d . , "Ana lytical Me th ods f or C oal and
C oa l Produc ts " , Academic Pre s s Jnc . , New Y ork , 1 97 9 , p J 6J . I
2 2 . Kamiya , Y . , Nage a , S . anp. Oikawa , S . , F ue l , 1 98J , 6 2 , J L
2 J . Harri s on , I . T . , Ch em . C omm . , 1 96 9 , 6 1 6 .
24 , R oye r , R . , Bache le t , J . P . f and Demers eman , P . , B ul l . S oc .
Chim . Fr . , 1 974 , 1 1 ( 2 ) , 2 6J 1 .
25 . Mc Carthy , J . R . , M o ore , J . L . and Cregge , R . J . , Te t t .
Le t t . , 1 97 8 , ,22._ , 5 1 8J .
2 6 . Pre s s , J . B . , Synth . C omm . , 1 97 9 , 2 ( 5 ) , 4 07 .
2 7 . M c Omi e , J .· F . W . , Wat ts , M . L . , and We s t , D . E . , Te trahe d
r on , 1 96 � , 24 , 2 2 8 9 . .
2 8 . Paul , W . L . and S chulman , S . G . , Ana l . Chim . Ac ta , 1 974
£2 , 1 95 .
? 9 · S tre i twe i s e r , A . Jr . , " S o lvolyti c D i s p laceme nt Re ac ti ons " ,
New Y ork , M c Graw -H i ll B o ok C ompany I nc . , 1 96 2 , p 1 ]: .
J O . K ov i , P . J . , M i l le r , C . L . and S ch ulman , S . G . , Ana l ,
Ch im . Ac ta . , 1 97 2 , .21_, 7 .
J l .. B·o s , · M �� D ahme n , E . A . , Ana l . Ch im . A c ta , 1 9 7 1 , 5 5 , 2 85 .
3 2 , Olm s t e ad , w . N . , Te trah e dr on , 1 97 1 , ..£2.. ( 1 3 ) , 2 7 1 3 ,
3 3 , F i s c h e r , A . , G a l l oway , w . J , and Vaughan , J . , J , Chem .
S o c , , 1 9 64 , 35 91 .
34 , Ware , W . R . , S h uk la , P . R . , S u l l ivan , P . J , and B r e mphi s ,
R . V . , J , Ch em . Phys . , 1 97 1 , 22. , 4 04 8 .
35 , Pa ta i , S . , E d . , " Th e C h e m i s try of Carb oxy l i c A c i d s and
E s te rs " , L o nd on , J ohn W i l e y and S ons , 1 96 9 , p 2 3 8 .
VI TA
Name : Jame s N i c o la s Ong S y .
Permanent A d d r e s s 5 1 6 N i c o d emus S t . , T ond o , M a n i l a , Ph i l .
D e gre e and d a t e t o be c onf e rre d M . S . Chemi s try , A ugus t 1 983
Date of B irth ' July 24 , 1 96 0
Pla c e o f B irth La oag C i ty , Ph i l ipp ine s
S e c ondary Educat i on S t . S te ph e n ' s H i gh S ch o o l .
C ollegiate I ns ti tuti ons A t te nded Date Degre e
Univers i ty of 'santo T omas { Ph i l . ) 6/7 7 -3/81 B . S . Chemi s try
Eas tern I l linois Univers i ty 6/82 - 8/83 M . S . Chemi s try
Ma j or Organi c Chemi� try
Pos i ti ons He ld
Re s e arch A s s i s tant
Graduate A s s i s tant
Date
6/8 1 -1 2/81
8/8 2 - 8/83
Ins t i t u t i o n
San M igue l C orpora t i on
Eas tern I l l ino i s Uni v .