United States: (12) Patent Application Publication (10) Pub. No.: US 2014/0073806 A1

US 20140073 806A1
( 12) Patent Application Publication ( 10) Pub. N o. : US 2014/0073806 A1

( 19 ) United States
Sas agawa et al. ( 43) Pub. D ate: Mar. 13, 2014
( 5 4) METHOD FOR PROD UCIN G EPOXY
COMPOUN D
( 71) Applicant: ArakaWa Ch em ical Indus tries , L td. ,
Os aka- s h i ( J P)
( 72) Inv entors : N aoki Sas agawa, Ts ukuba- s h i ( J P) ;
K iy os h i Takum i, Os aka- s h i ( J P) ;
Yoich iro Ez aki, Ts ukuba- s h i ( J P)
( 73) As s ignee: ArakaWa Ch em ical Indus tries , L td. ,
Os aka- s h i ( J P)
( 21) App1. N o. : 13/9 34, 078
( 22) Filed: J ul. 2, 2013
( 30) Foreign Application Priority D ata
J ul. 5 , 2012 ( J P) 2012- 15 1133
J ul. 1, 2013 ( J P) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2013- 138260
Publication Clas s i? cation
( 5 1) Int. Cl.
C07D 301/12 ( 2006. 01)
( 5 2) US. Cl.
CPC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C07D 301/12 ( 2013. 01)
USPC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 49 /5 31
( 5 7) ABSTRACT
To prov ide a m eth od f or producing an epoxy com pound h av
ing f ewer res idual q uaternary s alt com pound by rem ov ing th e
q uaternary s alt com pound f rom an organic s olution contain
ing an epoxy com pound and th e q uaternary s alt com pound.
A m eth od f or producing an epoxy com pound com pris ing th e
f ollowing s tep 1, s tep 2, and s tep 3:
s tep 1: a s tep in Wh ich in a m ixture liq uid containing an
ole? n com pound, an aq ueous h y drogen peroxide s olu
tion, a q uaternary s alt com pound, a h eteropoly acid, and
an organic s olv ent, th e ole? n com pound is s ubj ected to
th e oxidation reaction to obtain an organic s olution ( A)
containing an epoxy com pound,
s tep 2: a s tep in Wh ich an aq ueous inorganic alkali s olution
is alloWed to contact With th e organic s olution ( A) to
obtain an organic s olution ( B) containing th e epoxy
com pound, and
s tep 3: a s tep in Wh ich an acidic aq ueous s olution contain
ing a poly m er h av ing at leas t one f unctional group
s elected f rom th e group cons is ting of a carboxy l group
and a s ulf onic acid group is alloWed to contact With th e
organic s olution ( B) to obtain an organic s olution ( C)
containing th e epoxy com pound.
US 2014/0073806 A1
METHOD FOR PROD UCIN G EPOXY
COMPOUN D
FIEL D OF THE IN VEN TION
[ 0001] Th e pres ent inv ention relates to a m eth od f or pro
ducing an epoxy com pound With h y drogen peroxide and als o
relates to an epoxy com pound obtained by th e production
m eth od.
BACK GROUN D OF THE IN VEN TION
[ 0002] In general, an epoxy com pound are produced by
s ubj ecting an ole? n com pound to oxidation reaction in th e
pres ence of an organic peroxide s uch as peracetic acid or
perf orm ic acid, but in th is production m eth od, th ere are prob
lem s s uch th at th e organic peroxide is corros iv e, th e oxidation
reaction tends to be out of control, and an addition product of
th e organic peroxide as a by product rem ains in th e res ulting
epoxy com pound.
[ 0003] Th eref ore, a m eth od f or oxidiZ ing an ole? n com
pound With h y drogen peroxide in place of th e organic perox
ide h as been s tudied. Th is production m eth od is adv antageous
indus trially becaus e h y drogen peroxide as an oxidiZ ing agent
is not corros iv e, th e oxidation reaction is under control, and
th e by product is only Water.
[ 0004] HoWev er, it is di? icult to oxidiZ e ole? ns With h y dro
gen peroxide only . Th us , f or exam ple, in J P- A- 2004- 115 45 5 ,
J P- A- 2003- 19 2679 , Bull. Ch em . Soc. J pn. , 70, 9 05 - 9 15
( 19 9 7) , and J . Org. Ch em . , 61, 8310 ( 19 9 6) , a m eth od of
s ubj ecting an ole? n com pound to oxidation reaction ef f ec
tiv ely in an organic s olv ent containing an aq ueous h y drogen
peroxide s olution and a com bination of a q uaternary s alt
com pound and a h eteropoly acid is dis clos ed. HoWev er, a
large am ount of th e q uaternary s alt com pounds rem ain in th e
epoxy com pound obtained by th is production m eth od.
[ 0005 ] Th eref ore, f or exam ple, a m eth od Wh ere a ch em i
cally activ ated carbon is added to an organic s olution contain
ing an epoxy com pound and a q uaternary s alt com pound s o
th at th e q uaternary s alt com pound is ph y s ically ads orbed on
th e activ ated carbon is dis clos ed in J P- A- 2010- 70480. HoW
ev er, s ince th e activ ated carbon als o ads orbs oth er s ubs tances
in addition to th e q uaternary s alt com pound, its am ount us ed
is increas ed and th is is not econom ical.
[ 0006] MeanWh ile, th e q uaternary s alt com pound is als o
cons idered to be rem ov ed by v arious ch em ical ads orption
m eans . Such m eans include, f or exam ple, us e of an aq ueous
cy clodextrin s olution as des cribed in J P- A- 2008- 246287 and
us e of an ion exch ange res in as des cribed in J P- A- 2007
181833.
[ 0007] HoWev er, both m eans are intended to rem ov e a q ua
ternary s alt com pound contained in an aq ueous s olution and
are not s uitable f or rem ov al of a q uaternary s alt com pound
contained in an organic s olution. For exam ple, Wh en th e
aq ueous cy clodextrin s olution is added to an organic s olv ent
s olution containing an epoxy com pound and a q uaternary s alt
com pound, an em uls ion occurs , th eref or it becom es dif ? cult
or im pos s ible to rem ov e th e q uaternary s alt com pound. Fur
th er, s ince an ion exch ange res in is ty pically h y droph ilic and
dif ? cult to be Wet With an organic s olution, it is actually
dif ? cult to ads orb th e q uaternary s alt com pound contained
th erein on s uch a res in.
Mar. 13, 2014
PRIOR ART L ITERATURE
Patent D ocum ent
[ 0008] [ Patent docum ent 1] J P- A N o. 2004- 115 45 5
[ 0009 ] [ Patent docum ent 2] J P- A N o. 2003- 19 2679
[ 0010] [ Patent docum ent 3] J P- A N o. 2010- 70480
[ 0011] [ Patent docum ent 4] J P- A N o. 2008- 246287
[ 0012] [ Patent docum ent 5 ] J P- A N o. 2007- 181833
N on- Patent D ocum ent
[ 0013] [ N on- Patent docum ent 1] Bull. Ch em . Soc. J pn. , 70,
9 05 - 9 15 ( 19 9 7)
[ 0014] [ N on- Patent docum ent 2] ] . Org. Ch em . , 61, 8310
( 19 9 6)
SUMMARY OF THE IN VEN TION
Tech nical Problem
[ 0015 ] An obj ect of th e pres ent inv ention is to prov ide a
m eth od f or producing an epoxy com pound h av ing f eWer
res idual q uaternary s alt com pound by rem ov ing th e q uater
nary s alt com pound f rom an organic s olution containing an
epoxy com pound and th e q uaternary s alt com pound.
Solution to Problem
[ 0016] As a res ult of inv es tigation, th e pres ent inv entors
h av e f ound th at th e obj ect des cribed abov e can be ach iev ed by
s ubj ecting an ole? n com pound to oxidation reaction in a
m ixture liq uid containing an aq ueous h y drogen peroxide
s olution, a q uaternary s alt com pound, a h eteropoly acid, and
an organic s olv ent to obtain an organic s olution containing an
epoxy com pound and f urth er s ubj ecting th e organic s olution
to predeterm ined tWo s teps .
[ 0017] Th e pres ent inv ention relates to a m eth od f or pro
ducing an epoxy com pound com pris ing th e f olloWing s tep 1,
s tep 2, and s tep 3 and als o relates to an epoxy com pound
obtained by th e production m eth od.
[ 0018] A m eth od f or producing an epoxy com pound com
pris ing th e f olloWing s tep 1, s tep 2, and s tep 3:
[ 0019 ] s tep 1 : a s tep in Wh ich in a m ixture liq uid containing
an ole? n com pound, an aq ueous h y drogen peroxide s olution,
a q uaternary s alt com pound, a h eteropoly acid, and an organic
s olv ent, th e ole? n com pound is s ubj ected to th e oxidation
reaction to obtain an organic s olution ( A) containing an epoxy
com pound,
[ 0020] s tep 2: a s tep in Wh ich an aq ueous inorganic alkali
s olution is alloWed to contact With th e organic s olution ( A) to
obtain an organic s olution ( B) containing th e epoxy com
pound, and
[ 0021] s tep 3: a s tep in Wh ich an acidic aq ueous s olution
containing a poly m er h av ing at leas t one f unctional group
s elected f rom th e group cons is ting of a carboxy l group and a
s ulf onic acid group is alloWed to contact With th e organic
s olution ( B) to obtain an organic s olution ( C) containing th e
epoxy com pound.
Adv antageous Ef f ects of th e Inv ention
[ 0022] Since th e m eth od f or producing an epoxy com pound
according to th e pres ent inv ention includes th e s tep 1
des cribed abov e, it is pos s ible to conv ert v arious ole? n com
pounds , particularly cy clic ole? n com pounds th at are dif ? cult
to be s ubj ected to oxidation reaction due to th eir s teric h in
US 2014/0073806 A1
drance, into epoxy com pounds s af ely and e? iciently . More
ov er, additional prov is ion of th e predeterm ined s teps 2 and 3
af ter th e s tep 1 m akes it pos s ible to ? nally obtain a h igh - purity
epoxy com pound With f eWer res idual q uaternary s alt com
pound.
[ 0023] Th e epoxy com pound obtained by th e production
m eth od of th e pres ent inv ention is us ef ul as interm ediates f or
ph arm aceuticals and agroch em icals ; raW m aterials f or v ari
ous perf um es and poly m ers ; s em iconductor m aterials and
raW m aterials f or electric/electronic m aterials ; reactiv e dilu
ents ; s ealants ; detergents ; poly m er m odi? ers ; ink com po
nents f or ph otocurable inkj et; and raW m aterials f or coating
m aterials , adh es iv es , and res is ts .
D ESCRIPTION OF EMBOD IMEN TS
[ 0024] Th e production m eth od of th e pres ent inv ention is
ch aracteriz ed by including th e f olloWing s tep 1, s tep 2, and
s tep 3.
[ 0025 ] s tep 1 : a s tep in Wh ich in a m ixture liq uid containing
an ole? n com pound, an aq ueous h y drogen peroxide s olution,
a q uaternary s alt com pound, a h eteropoly acid, and an organic
s olv ent, th e ole? n com pound is s ubj ected to th e oxidation
reaction to obtain an organic s olution ( A) containing an epoxy
com pound,
[ 0026] s tep 2: a s tep in Wh ich an aq ueous inorganic alkali
s olution is alloWed to contact With th e organic s olution ( A) to
obtain an organic s olution ( B) containing th e epoxy com
pound, and
[ 0027] s tep 3: a s tep in Wh ich an acidic aq ueous s olution
containing a poly m er h av ing at leas t one f unctional group
s elected f rom th e group cons is ting of a carboxy l group and a
s ulf onic acid group is alloWed to contact With th e organic
s olution ( B) to obtain an organic s olution ( C) containing th e
epoxy com pound.
[ 0028] Th e s tep 1 is a s tep of oxidiZ ing an ole? n com pound
as a s ubs trate to conv ert into an epoxy com pound.
[ 0029 ] As th e ole? n com pound, v arious knoWn ole? n com
pounds can be us ed With out particular lim itation as long as
th ey are uns aturated h y drocarbons h av ing at leas t one carbon
carbon double bond in th e m olecule. Furth er, th e pos ition of
th e carbon- carbon double bond in th e ole? n com pound is not
particularly lim ited, and s uch a double bond m ay be located at
th e m olecular ends and/or With in th e m olecule of th e ole? n
com pound.
[ 0030] Furth er, th e ole? n com pound m ay h av e a v ariety of
s ubs tituents . Exam ples of th e s ubs tituent include h y drocar
bon groups ( e. g. , alky l group, alkeny l group, ary l group, and
alkoxy group) ; polar groups ( e. g. , h y droxy l group, carboxy l
group, m ercapto group, am ino group, am ino group s ubs ti
tuted With th e h y drocarbon group, am ide group, nitro group,
cy ano group, acy l group, es ter group, eth er group, epoxy
group, and carbony l group) ; h eterocy clic s tructure- contain
ing groups ; h alogen atom s ; and th e like. Hereinaf ter, th e s am e
s h all apply to th e s ubs tituent .
[ 0031] Exam ples of th e alky l group include linear alky l
groups ( e. g. , m eth y l group, eth y l group, n- propy l group,
n- buty l group, n- penty l group, n- h exy l group, n- octy l group,
n- nony l group, and n- decy l group) ; branch ed alky l groups
( e. g. , is opropy l group, is obuty l group, s ec- buty l group, tert
buty l group, and is oocty l group) ; cy cloalky l groups ( e. g. ,
cy clobuty l group, cy clopenty l group, cy cloh exy l group,
cy cloh epty l group, cy cloocty l group, cy clonony l group,
cy clodecy l group, cy clododecy l group, and norbom y l group) ;
and th e like.
Mar. 13, 2014
[ 0032] Exam ples of th e alkeny l group include linear alk
eny l groups ( e. g. , eth eny l group, n- buteny l group, n- propeny l
group, n- penteny l group, n- h exeny l group, n- octeny l group,
n- noneny l group, and n- deceny l group) ; branch ed alkeny l
groups ( e. g. , is opropeny l group, is obuteny l group, s ec- bute
ny l group, tert- buteny l group, and is oocteny l group) ;
cy cloalkeny l groups ( e. g. , cy clopenteny l group, cy cloh exeny l
group, cy cloh epteny l group, cy cloocteny l group and nor
borneny l group) ; and th e like.
[ 0033] Exam ples of th e ary l group include ph eny l groups
and naph th y l groups . In addition, th e ary l group m ay h av e th e
s ubs tituent. Speci? c exam ples of th e ary l group h av ing th e
s ubs tituent include a 2- ? uoroph eny l group, a 3- ? uoroph eny l
group, a 4- ? uoroph eny l group, a 2- ch loroph eny l group, a
3- ch loroph eny l group, a 4- ch loroph eny l group, a 2- bro
m oph eny l group, a 2- m eth y lph eny l group, a 4- m eth y lph eny l
group, a 4- m eth oxy ph eny l group, a 4- acety lph eny l group,
and th e like.
[ 0034] Th e alkoxy groups include, in addition to alkoxy
groups With about 1 to 10 carbon atom s ( e. g. , m eth oxy group,
eth oxy group, propoxy group, butoxy group, t- butoxy group,
cy cloh exy loxy group, and penty loxy group) , ph enoxy
groups , benZ y loxy groups , naph th y loxy groups , and th e like.
[ 0035 ] Exam ples of th e h eterocy clic s tructure- containing
group include groups deriv ed f rom h eterocy clic com pounds
s uch as aZ iridine, oxirane, th iirane, aZ irine, oxirene, th iirene,
aZ etidine, oxetane, th ietane, aZ ete, aZ olidine, oxolane, th i
olane, aZ ole, oxol, th iol, aZ ine, oxane, th iane, py ridine, py ry
lium ions , th iopy ry lium ions , aZ epane, oxepane, th iepane,
aZ epine, oxepine, th iepine, im idaZ ole, py raZ ole, oxaZ ole,
th iaZ ole, im idaZ oline, py raZ ine, m orph oline, th iaZ ine, indole,
is oindole, benZ oim idaZ ole, purine, q uinoline, is oq uinoline,
q uinoxaline, cinnoline, pteridine, and benZ opy ran.
[ 0036] Exam ples of th e h alogen atom include ? uorine,
ch lorine, brom ine, and iodine.
[ 0037] Am ong th e ole? n com pounds , th e production
m eth od of th e pres ent inv ention is s uitable particularly f or th e
epoxidation of ( a) an ole? n com pound th at is dif ? cult to be
s ubj ected to oxidation reaction becaus e of large s teric h in
drance around th e carbon- carbon double bond th at is a reac
tiv e s ite and ( b) an ole? n com pound th at is dif ? cult to enh ance
its purity by knoWn dis tillation puri? cation m eans becaus e of
loW v olatility of th e epoxy com pound obtained, th ough th e
epoxidation its elf of th e carbon- carbon double bond th at is a
reactiv e s ite is eas ily perf orm ed. Exam ples of s uch an ole? n
com pound include v arious cy clic ole? n com pounds and/or
long- ch ain linear ole? n com pounds .
[ 0038] Th e cy clic ole? n com pounds include ole? n com
pounds h av ing at leas t one s keleton s elected f rom th e group
cons is ting of th e cy cloalky l group and th e cy cloalkeny l group
in th e m olecule. Furth er, one or tWo or m ore of th e s ubs titu
ents m ay be bonded to th e cy cloalky l group and th e cy cloalk
eny l group, and exam ples of s uch a s ubs tituent include h y dro
carbon groups ( e. g. , alky l group With about 1 to 5 carbon
atom s and alkeny l group With about 2 to 5 carbon atom s ) and
polar groups ( e. g. , h y droxy l group and es ter group) .
[ 0039 ] Speci? c s pecies of th e cy clic ole? n com pound
include an ole? n com pound repres ented by th e f olloWing
general f orm ula ( 1) , an ole? n com pound repres ented by th e
f olloWing general f orm ula ( 2) , an ole? n com pound repre
s ented by th e f olloWing general f orm ula ( 3) , an ole? n com
pound repres ented by th e f olloWing general f orm ula ( 4) , an
ole? n com pound repres ented by th e f olloWing general f or
m ula ( 5 ) , an ole? n com pound repres ented by th e f olloWing
US 2014/0073806 A1
general f orm ula ( 6) , and Various known terpene- bas ed ole? n
com pounds . Howev er, th os e corres ponding to th e terpene
bas ed ole? n com pounds are excluded f rom th e ole? n com
pound repres ented by th e general f orm ula ( 4)
General f orm ula ( 1)
[ Form ula 1]
R7 Rs 0 R11 R12
R9 R10
R6 R13
0
R1 R18
R5 R2 R17 R14
R4 R3 R16 R15
( Wh erein, R1, R2, R3, R4, R5 , R6, R7, R8, R9 , R10, R11, R12,
R13, R14, R15 , R16, R17, and R18 each repres ent a h y drogen
atom or th e s ubs tituent. In addition, m l and m 2 each repres ent
0 or 1. Furth er, Wh en m l is 1, th is m eans th at a m eth y lene
group is pres ent in th e cros s linked f orm in th e ring, and Wh en
m l is 0, th is m eans th at a m eth y lene group is not pres ent in th e
ring. In addition, Wh en m 2 is 1, th is m eans th at a m eth y lene
m 2 is 0, th is m eans th at a m eth y lene group is not pres ent in th e
ring. HoWeVer, Wh en m l is 1, eith er or both of R3 and R4 are
h y drogen, and eith er or both of R7 and R8 are h y drogen. Als o,
Wh en m 2 is 1, eith er or both of R1 1 and R12 are h y drogen, and
eith er or both of R15 and R16 are h y drogen. )
24 25 0 [ Form ula 2]
R R R26
R23 R27
0/
R22 R19
R21 R20
( Wh erein, R19 , R20, R21, R22, R23, R24, R25 , R26 and R27 each
repres ent a h y drogen atom or th e s ubs tituent. In addition, n
repres ents 0 or 1, and Wh en n is 1, th is m eans th at a m eth y lene
n is 0, th is m eans th at a m eth y lene group is not pres ent in th e
ring. HoWeVer, Wh en n is 1, eith er or both of R21 and R22 are
h y drogen, and eith er or both of R24 and R25 are h y drogen. )
[ Form ula 3]
R29 R28
( wh erein R28 R29 R3 R31 R32 R33 R34 R3 R36 R3 R38
and R39 each repres ent a h y drogen atom or th e s ubs tituent. In
Mar. 13, 2014
addition, p repres ents 0 or 1, and Wh en p is 1, th is m eans th at
a m eth y lene group is pres ent in th e cros s linked f orm in th e
ring, and Wh en p is 0, th is m eans th at a m eth y lene group is not
pres ent in th e ring. HoWeVer, Wh en p is 1, eith er or both of R28
and R29 are h y drogen, and eith er or both of R32 and R33 are
h y drogen. Furth er, th e das h ed line repres ents a carbon- carbon
s ingle bond or a carbon- carbon double bond. )
[ Form ula 4]
( Wh erein, R40, R41, R42, R43, R44, R45 , R46, R47, R48, R49 and
R5 0 each repres ent a h y drogen atom or th e s ubs tituent. In
addition, q repres ents 0 or 1, and Wh en q is 1, th is m eans th at
ring, and Wh en q is 0, th is m eans th at a m eth y lene group is not
pres ent in th e ring. HoWeVer, Wh en q is 1, eith er or both of R42
h y drogen. Furth er, th e das h ed line repres ents a carbon- carbon
s ingle bond or a carbon- carbon double bond. )
General f orm ula ( 5 )
[ Form ula 5 ]
R5 5 R5 6
R5 4 \R5 7
R5 8
R5 3 R5 1
R5 2
( Wh erein, R5 1, R5 2, R5 3, R5 4, R5 5 , R5 6, R5 7 and R5 8 each
repres ent a h y drogen atom or th e s ubs tituent. )
General f orm ula ( 6) :
[ Form ula 6]
R62 R63 R64
( Wh erein, R5 9 , R60, R61, R62, R63, R64, R65 and R66 each
[ 0040] Speci? c exam ples of th e s ubs tituent in th e general
f orm ulas ( l) , ( 2) , ( 3) , ( 4) , ( 5 ) , and ( 6) include pref erably alky l
groups With about 1 to 5 carbon atom s am ong th e alky l groups
des cribed abov e, th e polar groups ( e. g. , h alogen and h y droxy l
group) , and th e like.
US 2014/0073806 A1
[ 0041] Th e terpene- bas ed ole? n com pound ref ers to a
h y drocarbon com pound repres ented by ( C5 H8) , ( r is an inte
ger) , a deriv ativ e deriv ed f rom th e h y drocarbon, and a com
pound h av ing a dif f erent num ber of double bonds and a
dif f erent uns aturation degree f rom th e f oregoing. Speci? c
exam ples th ereof include oligom ers ( e. g. , terpene h y drocar
bon, terpene alcoh ol, terpene aldeh y de, terpene ketone, ter
pene dim er, terpene trim er, and terpene tetram er) , oth er com
pounds , and th e like. Exam ples of th e terpene h y drocarbon
include m onoterpenes ( e. g. , ot- pinene, [ 3- pinene, lim onene,
ot- ph ellandrene, [ 3- ph ellandrene, ot- terpinene, y - terpinene,
o- cim ene, m y rcene, cam ph ene, terpinolene, s y lv es trene, s ab
inene, carene, tricy clene, and f ench ene) ; s es q uiterpenes ( e. g. ,
longif olene, cary oph y llene, is ocary oph y llene, arom aden
drene, bis abolene, s antalene, Z ingiberene, curcum ene,
cadinene, s es q uibenih ene, and cedrene) ; diterpenes ( e. g. ,
cam ph olene, podocarprene, m irene, ph y llocladene, and total
ene) ; and th e like. Th e terpene deriv ativ es include 1- carv one,
s obrerole, geraniol, gerany l acetate, citronelly l acetate, terpi
ny l acetate, citral, citronellal, citronellol, dih y drom y rcenol,
and linalool, and oth er com pounds obtained by th e reaction of
th e terpene h y drocarbon as a raW m aterial, and th e like. In
addition, th e terpene- bas ed ole? n com pounds include optical
is om ers . Exam ples of th e optical is om er of th e ot- pinene
include ( 1R) - ( + ) - 0t- pinene and ( 1 S) - ( ) - 0t- pinene. In cas e of
th e lim onene, th e optical is om ers include ( l) - lim onene and
( d) - lim onene. Furth er, th e lim onene deriv ativ es include
lim onene- 1, 2- oxide.
[ 0042] Exam ples of th e long- ch ain linear ole? n com pound
include com pounds repres ented by th e f olloWing general f or
m ula ( 7) ( prov ided th at th e com pounds repres ented by th e
general f orm ulas ( 1) , ( 2) , ( 3) , ( 4) , ( 5 ) , and ( 6) , and com pounds
corres ponding to th e terpene- bas ed ole? n com pounds are
excluded) .
[ Form ula 7]
R68 R69
R67 R70
( Wh erein, R67, R68, R69 , and R70 each repres ent a h y drogen
atom or an alky l group With about 3 to 30 carbon atom s ,
pref erably about 6 to 30 carbon atom s ( prov ided th at a
cy cloalky l group is excluded) or an alkeny l group With about
3 to 30 carbon atom s , pref erably about 6 to 30 carbon atom s
( prov ided th at a cy cloalkeny l group is excluded) With th e
prov is o th at th e cas e Wh ere R7, R68, R69 , and R70 are all
h y drogen is excluded. Th e num ber of carbon- carbon double
bond( s ) contained in th e alkeny l group is about 1 to 3. In
addition, th e alky l group and th e alkeny l group m ay h av e th e
s ubs tituent ( s ) as des cribed abov e. )
[ 0043] Speci? c exam ples of th e com pound repres ented by
th e general f orm ula ( 7) include linear ot- ole? ns With about 6
to 30 carbon atom s ( e. g. , 1- h exene, 1- h eptene, 1- octene,
1- nonene, 1- decene, 1- dodecene, 1- tetradecene, 1- penta
decene, 1- h exadecene, 1- octadecene, 1- eicocene, 1- do
cocene, 1- tetracocene, 1- octacocene, and 1- triacontene) ,
branch ed ot- ole? ns ( e. g. , 2, 4, 4- trim eth y l- 1- pentene. ) , corre
s ponding internal ole? ns th ereof , and th e like. Furth er, th e
linear ot- ole? ns and th e internal ole? ns m ay h av e th e s ubs titu
ent ( s ) as m entioned abov e.
Mar. 13, 2014
[ 0044] Th e ole? n com pound us ed in th e pres ent inv ention
m ay be a pure product or a m ixture of plural ole? n com
pounds , or m ay be a m ixture of geom etrical is om ers and
optical is om ers .
[ 0045 ] Th e aq ueous h y drogen peroxide s olution acts as an
oxidiZ ing agent f or ole? n com pounds . Th e concentration
th ereof is not particularly lim ited, but it is us ually about 0. 1 to
100% by Weigh t, pref erably about 1 to 80% by Weigh t, and
f urth er pref erably about 10 to 60% by Weigh t.
[ 0046] Th e am ount us ed of th e aq ueous h y drogen peroxide
s olution is not particularly lim ited, but h y drogen peroxide is
us ually us ed With in a range of about 0. 001 to 10 eq uiv alents ,
pref erably about 0. 01 to 5 eq uiv alents , and m ore pref erably
about 0. 1 to 2 eq uiv alents , per one carbon- carbon double
bond contained in th e ole? n com pound. In th e cas e Wh ere th e
ole? n com pound h as tWo or m ore carbon- carbon double
bonds , an epoxy com pound in Wh ich th e res ulting carbon
carbon double bond rem ains can be obtained by appropriately
ch anging th e am ount us ed of th e aq ueous h y drogen peroxide
s olution.
[ 0047] Various knoWn com pounds can be us ed as th e q ua
ternary s alt com pound With out any particular lim itation, and
in particular, q uaternary cationic s pecies repres ented by th e
f olloWing general f orm ula ( 8) is pref erable.
[ Form ula 8]
( Wh erein, R7 1, R72, R73 , and R74 m ay be th e s am e or dif f erent,
and each repres ent th e alky l group, alkeny l group, or ph eny l
group as des cribed abov e. In addition, th e alky l or alkeny l
group m ay be bonded to th e ph eny l group. Furth er, X repre
s ents a nitrogen atom or a ph os ph orus atom . )
[ 0048] Th e num ber of th e carbon atom s of th e alky l or
alkeny l group cons tituting R71, R72, R73, and R74, res pec
tiv ely is not particularly lim ited, and is us ually about 6 to 20.
[ 0049 ] In addition, exam ples of anionic s pecies th at f orm s
a pair With th e q uaternary cationic s pecies include ch loride
ions , brom ide ions , iodide ions , h y droxide ions , nitrate ions ,
s ulf ate ions , h y drogen s ulf ate ions , acetate ions , carbonate
ions , h y drogen carbonate ions , ph os ph ate ions , h y drogen
ph os ph ate ions , and th e like.
[ 005 0] Exam ples of th e q uaternary s alt com pound in Wh ich
X is a nitrogen atom include a triocty lm eth y l am m onium s alt,
a triocty leth y l am m onium s alt, a tridecany lm eth y l am m o
nium s alt, a trialky lm eth y l ( m ixed ty pe of octy l group and
decany l group) am m onium s alt, a trih exadecy lm eth y l am m o
nium s alt, a dialky ldim eth y l ( m ixed ty pe of C8 to C18 alky l
ch ains ) am m onium s alt, a dilaury ldim eth y l am m onium s alt, a
didecy ldim eth y l am m onium s alt, a diocty ldim eth y l am m o
nium s alt, a dioley ldim eth y l am m onium s alt, a laury ltrim
eth y l am m onium s alt, a s teary ltrim eth y l am m onium s alt, a
laury ldim eth y lbenZ y l am m onium s alt, a dis teary ldim eth y l
am m onium s alt, a tetrabuty l am m onium s alt, a benZ y ltrim
eth y l am m onium s alt, a benZ y ltrieth y l am m onium s alt, a ben
Z y ltributy l am m onium s alt, a tetrapenty l am m onium s alt, a
tetrabuty lam m onium s alt, a tetram eth y lam m onium s alt, and
th e like, and th es e s alts can be us ed alone or in com bination of
US 2014/0073806 A1
tWo or m ore kinds th ereof . Furth er, th e dialky ldim eth y l
( m ixed ty pe of C8 to C18 alky l ch ains ) am m onium s alt
ref ers s peci? cally to an am m onium s alt in Wh ich th e alky l
group is deriv ed f rom coconut oil ( th e s am e s h all apply h ere
inaf ter) , and, exam ples th ereof include ARQUAD 2C- 75
( trade nam e) m anuf actured by L ion Corporation.
[ 005 1] Exam ples of th e q uaternary s alt com pound in Wh ich
X is a ph os ph orus atom include tetraph eny l ph os ph onium ,
tetra- n- eth y l ph os ph onium , tetra- n- propy l ph os ph onium ,
tetra- n- buty l ph os ph onium , di- n- decy ldim eth y l ph os ph o
nium , di- n- octadecy ldim eth y l ph os ph onium , tri- n- decy lm
eth y l ph os ph onium , benZ y ltributy l ph os ph onium , ph eny ltri
m eth y l ph o s ph onium , tetraph eny l ph o s ph onium , and th e like,
and th es e ph os ph onium s m ay be us ed alone or in com bination
of tWo or m ore kinds th ereof .
[ 005 2] As th e q uaternary s alt com pound, a q uaternary
am m onium s alt com pound h av ing at leas t one alky l group
With about 6 to 20 carbon atom s in th e m olecule, particularly
a q uaternary am m onium s alt com pound h av ing 2 to 3 s uch
alky l groups is pref erable f rom th e v ieWpoint of res training an
am m onium s alt com pound f rom rem aining in th e target
epoxy com pound. Speci? c exam ples of th e q uaternary
am m onium s alt com pound include pref erably th e triocty lm
eth y l am m onium s alt, th e trialky lm eth y l ( m ixed ty pe of octy l
group and decany l group) am m onium s alt, th e dialky ldim
eth y l ( m ixed ty pe of C8 to C18 alky l ch ains ) am m onium s alt,
th e dilaury ldim eth y l am m onium s alt, th e didecy ldim eth y l
am m onium s alt, th e diocty ldim eth y l am m onium s alt, and th e
like, and th es e am m onium s alts m ay be us ed alone or in
com bination of tWo or m ore kinds th ereof . In addition, as th e
anionic s pecies th at f orm s each am m onium s alt, one or tWo or
m ore kinds of anionic s pecies s elected f rom ch loride ions ,
carbonate ions , acetate ions , h y drogen s ul? te ions , and th e
like are pref erable.
[ 005 3] Th e am ount us ed of th e q uaternary s alt com pound is
not particularly lim ited, but th e q uaternary s alt com pound is
us ually us ed in an am ount of about 0. 0001 to 20 m oles ,
pref erably about 0. 001 to 15 m oles , and m ore pref erably
about 0. 01 to 10 m oles , per 100 m oles of th e ole? n com
pound.
[ 005 4] In th e production m eth od of th e pres ent inv ention,
th e h eteropoly acid is a com pound th at acts as an oxidiZ ing
agent f or ole? ns togeth er With th e aq ueous h y drogen perox
ide s olution, and is obtained by introducing a h etero atom into
v arious knoWn is opoly acids or m etal s alts th ereof .
[ 005 5 ] Th e is opoly acids include inorganic acids m ainly
com pos ed of inorganic elem ents ( e. g. , tungs ten, m oly bde
num , ch rom ium , m anganes e, v anadium , niobium , rh enium ,
iron, ruth enium , cobalt, nickel, palladium , platinum , copper,
s ilv er, gold, tin, titanium , Z irconium , rh odium , iridium ,
os m ium , and Z inc) and s alts th ereof .
[ 005 6] In addition, th e h etero atom s include oxy gen, s ulf ur,
ph os ph orus , am m onium , potas s ium , s odium , and th e like.
[ 005 7] As th e h eteropoly acid, a tungs ten- bas ed h eteropoly
acid obtained by introducing ph os ph orus into a tungs ten
containing is opoly acid and a m oly bdenum - bas ed h eteropoly
acid obtained by introducing ph os ph orus into a m oly bdenum
containing is opoly acid are pref erable f rom th e point th at
epoxidation of th e ole? n com pound, particularly th e cy clic
ole? n com pound, is eas ily ach iev ed.
[ 005 8] Th e tungs ten- bas ed h eteropoly acids include tung
s tic acid, tungs ten trioxide, tungs ten tris ul? de, tungs ten ph os
ph ate, am m onium tungs tate, potas s ium tungs tate ( dih y drate) ,
12- ph os ph otungs tic acid ( h y drate) , and s odium tungs tate ( di
Mar. 13, 2014
h y drate) . Of th es e, tungs tic acid, tungs ten trioxide, tungs ten
ph os ph ate, and s odium tungs tate ( dih y drate) are pref erable,
and in particular, tungs tic acid, 12- ph os ph otungs tic acid ( h y
drate) , s odium tungs tate ( dih y drate) , and ph os ph otungs tic
acid are pref erable. Th es e acids m ay be us ed alone or in
com bination of tWo or m ore kinds th ereof .
[ 005 9 ] Th e m oly bdenum - bas ed h eteropoly acids include
m oly bdic acid and ph os ph om oly bdic acid. Furth er, th es e m ay
be h y drates .
[ 0060] As th e h eteropoly acid in th e pres ent inv ention, it is
als o pos s ible to us e th e reaction product of a h etero atom
donor With is opoly acid or a s alt th ereof , in addition to com
m ercially av ailable products as th ey are. In addition,
exam ples of th e h etero atom donor include ph os ph oric acids
s uch as ph os ph oric acids , ph os ph onic acids , and s alts th ereof .
[ 0061] Exam ples of th e ph os ph oric acids include ph os ph o
ric acid, poly ph os ph oric acid, py roph os ph oric acid, h exam
etaph os ph oric acid, h y poph os ph orous acid, ph os ph orous
acid, dodecy lph os ph oric acid, 2- eth y lh exy lph os ph oric acid,
and th e like; and exam ples of th e ph os ph oric acid s alts
include s odium ph os ph ate, potas s ium ph os ph ate, am m onium
ph os ph ate, s odium dih y drogen ph os ph ate, dis odium h y dro
gen ph os ph ate, potas s ium h y drogen ph os ph ate, am m onium
h y drogen ph os ph ate, s odium poly ph o s ph ate, s odium h exam
etaph os ph ate, acidic s odium h exam etaph os ph ate, s odium
py roph os ph ate, dis odium dih y drogen py roph os ph ate,
s odium h y poph os ph ite, s odium ph os ph ite, and th e like. Fur
th er, exam ples of th e ph os ph onic acids include m eth y lph os
ph onic acid, eth y lph os ph onic acid, n- propy lph os ph onic acid,
is opropy lph os ph onic acid, n- buty lph os ph onic acid, t- bu
ty lph os ph onic acid, ph eny lph os ph onic acid, 4- m eth oxy ph e
ny lph os ph onic acid, 4- am inoph eny lph os ph onic acid, 1- h y
droxy eth ane- 1 , 1 - bis ( ph o s ph onic acid) , nitrilotris
( m eth y leneph os ph onic acid) , and th e like. Moreov er,
exam ples of th e s alts of th e ph os ph onic acids include s odium
ph eny lph os ph onate and th e like. Am ong th es e, ph os ph oric
acid, ph eny lph os ph onic acid, ph os ph orous acid, h y poph os
ph orous acid, 2- eth y lh exy lph os ph oric acid, laury l ph os ph ate,
s odium dih y drogen ph os ph ate, and th e like are pref erable.
[ 0062] Th e am ount us ed of th e h eteropoly acid is not par
ticularly lim ited, but it is us ually about 0. 0001 to 20 m oles ,
pref erably about 0. 001 to 15 m oles , and m ore pref erably
about 0. 01 to 10 m oles , per 100 m oles of th e ole? n com
pound. If th e ole? n com pound h as tWo or m ore carbon- carbon
double bonds , it is als o pos s ible to obtain an epoxy com pound
in Wh ich th e res ulting carbon- carbon double bond rem ains by
appropriately ch anging th e am ount us ed of th e h eteropoly
acid.
[ 0063] Furth er, Wh en th e reaction product of th e h etero
atom donor With th e is opoly acid or a s alt th ereof is us ed as th e
h eteropoly acid, th e am ount us ed of th e is opoly acid is about
0. 0001 to m oles , pref erably about 0. 001 to 15 m oles , and
m ore pref erably about 0. 01 to 10 m oles , per 100 m oles of th e
ole? n com pound. In addition, th e am ount us ed of th e h etero
atom donor ( e. g. , ph os ph oric acids ) is about 0. 0001 to 10
m oles , pref erably about 0. 001 to 15 m oles , and m ore pref er
ably about 0. 01 to 10 m oles , bas ed on th e ole? n com pound.
[ 0064] Th e organic s olv ent is not particularly lim ited as
long as it is s paringly s oluble or ins oluble in Water and acts as
a s olv ent f or liq uid- liq uid extraction. Speci? c exam ples
th ereof include arom atic h y drocarbon- bas ed organic s olv ents
( e. g. , toluene and xy lene) ; ch lorinated organic s olv ents ( e. g. ,
ch lorof orm , ch lorobenZ ene, o- dich lorobenZ ene, dich loro
toluene, dich lorom eth ane, and dich loroeth ane) ; alicy clic
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organic s olv ents ( e. g. , h exane and cy cloh exane) ; es ter- bas ed
organic s olv ents ( e. g. , eth y lacetate and buty l acetate) ; and
eth er- bas ed organic s olv ents ( e. g. , dieth y l eth er) . Of th es e,
Wh en th e arom atic h y drocarbon- bas ed organic s olv ent, in
particular toluene, is us ed, th e q uaternary s alt com pound is
h ard to rem ain in th e res ulting epoxy com pound. Th e am ount
us ed of th e organic s olv ent is not particularly lim ited, and
m ay be appropriately s et.
[ 0065 ] In th e s tep 1, af ter s ubj ecting th e ole? n com pound to
oxidation reaction in a m ixture liq uid containing th e ole? n
com pound, aq ueous h y drogen peroxide s olution, q uaternary
s alt com pound, h eteropoly acid, and organic s olv ent, th e
res ulting s olution is s eparated into an aq ueous ph as e and an
organic ph as e. Th en, th is organic ph as e is regarded as an
organic s olution ( A) containing th e epoxy com pound.
[ 0066] Th e order of th e addition of th e ole? n com pound,
aq ueous h y drogen peroxide s olution, q uaternary s alt com
pound, h eteropoly acid, and organic s olv ent to th e reaction
s y s tem in th e s tep 1 is not particularly lim ited. Th ere are
exem pli? ed a m eth od Wh ere all th e com ponents are ch arged
into a s uitable reaction v es s el at a tim e and a m eth od Wh ere an
aq ueous cataly s t s olution containing th e aq ueous h y drogen
peroxide s olution, q uaternary s alt com pound, and h eteropoly
acid is prepared once, and th en an organic s olution containing
th e ole? n com pound and organic s olv ent is added to th e
cataly s t s olution, f olloWed by s tirring and m ixing th e entire
reaction s y s tem . Th e q uaternary s alt com pound acts as a
ph as e trans f er cataly s t. Th e is opoly acid and th e h etero atom
donor ( e. g. , ph os ph oric acids ) m ay be us ed independently in
place of th e h eteropoly acid, and, in th is cas e, a h eteropoly
acid is produced in th e reaction s y s tem .
[ 0067] In addition, th e reaction s y s tem is a tWo- ph as e m ix
ture s y s tem , and ph as e s eparation betWeen th e organic ph as e
and th e aq ueous ph as e occurs by leav ing th e reaction s y s tem
as it is . At th is tim e, th e pH of th e aq ueous ph as e is us ually
about 0. 1 to 7, pref erably about 0. 5 to 4. 0 f rom th e v ieWpoint
of im prov ing th e rate of th e epoxidation reaction or s uppres s
ing th e f orm ation of by products . Exam ples of th e pH adj us t
ing m eans include acids ( e. g. , s ulf uric acid) , acidic s alts ( e. g. ,
ph os ph ate) , alkali m etal h y droxides ( e. g. , s odium h y drox
ide) , and th e like. Th en, af ter th e com pletion of th e oxidation
reaction, an organic s olution ( A) is obtained by rem ov ing th e
aq ueous ph as e of th e aq ueous and organic ph as es or collect
ing th e organic ph as e.
[ 0068] Th e conditions in th e oxidation reaction in th e s tep 1
are not particularly lim ited. Us ually , th e reaction tem perature
is about 30 C. to 140 C. , pref erably about 00 C. to 80 C. ,
and m ore pref erably about 20 C. to 60 C. Furth er, th e
reaction tim e is us ually about 30 m inutes to 24 h ours , pref
erably about 1 to 20 h ours , and m ore pref erably about 2 to 12
h ours . In addition, th e pres s ure during th e reaction is us ually
about 80 kPa to 1 MPa.
[ 0069 ] In th e s tep 1 of th e pres ent inv ention, v arious knoWn
neutral inorganic s alts m ay be pres ent in th e m ixture liq uid,
Wh ich is th e oxidation reaction s y s tem of th e ole? n com
pound. Th e us e of th e neutral inorganic s alt m akes it pos s ible
to prev ent is om eriZ ation or degradation of an epoxy com
pound particularly uns table to acids and h eat am ong th e
epoxy com pounds deriv ed f rom th e ole? n com pound.
Exam ples of th e epoxy com pound include th e epoxy com
pound obtained f rom th e ole? n com pound repres ented by th e
general f orm ula ( 4) and th e epoxy com pound obtained f rom
th e terpene- bas ed com pound. Th e neutral inorganic s alt is
pref erably s ulf ates and exam ples of th e s ulf ates include
Mar. 13, 2014
lith ium s ulf ate, s odium s ulf ate, potas s ium s ulf ate, calcium
s ulf ate, m agnes ium s ulf ate, and th e like. Th e am ount us ed of
th e neutral inorganic s alt is not particularly lim ited, but it is
us ually about 1 to 5 00 m oles , pref erably about 5 to 25 0 m oles ,
and m ore pref erably about 10 to 100 m oles , per 100 m oles of
th e ole? n com pound.
[ 0070] Furth er, af ter th e com pletion of th e s tep 1, f or
exam ple, an aq ueous s olution of s odium th ios ulf ate or th e like
as a s ubs tance f or decom pos ing h y drogen peroxide rem ain
ing in th e organic s olution ( A) m ay be added to th e organic
s olution ( A) bef ore th e s tep 2. Als o, th e epoxy com pound
contained in th e organic s olution ( A) m ay be once is olated by
knoWn puri? cation m eans s uch as dis tillation, and a s olution
obtained by dis s olv ing th e is olated product again in th e
organic s olv ent can be regarded as th e organic s olution ( A) .
[ 0071] Th e s tep 2 is a s tep to obtain an organic s olution ( B)
containing th e epoxy com pound af ter contacting an aq ueous
inorganic alkali s olution With th e organic s olution ( A) . Spe
ci? cally , af ter m ixing th e organic s olution ( A) With v arious
knoWn aq ueous inorganic alkali s olution, th e res ulting s olu
tion is s eparated into an aq ueous ph as e and an organic ph as e.
Th en, an organic s olution ( B) containing th e epoxy com
pound is obtained by rem ov ing th e aq ueous ph as e or collect
ing th e organic ph as e. Th is s tep is a s o- called a Was h ing s tep,
and, as a res ult of trans f er of Water- s oluble s ubs tances s uch as
h eteropoly acids contained in th e organic s olution ( A) to th e
aq ueous inorganic alkali s olution, th e concentration of th e
epoxy com pound in th e res ulting organic s olution ( B) is
increas ed.
[ 0072] Exam ples of th e aq ueous inorganic alkali s olution
include aq ueous s olutions of s odium h y droxide, potas s ium
h y droxide, lith ium h y droxide, calcium h y droxide, am m o
nium h y droxide, tetram eth y l am m onium h y droxide, s odium
ph os ph ate, potas s ium ph os ph ate, lith ium ph os ph ate, calcium
ph os ph ate, s odium carbonate, potas s ium carbonate, lith ium
carbonate, calcium carbonate, s odium h y drogen carbonate,
s odium acetate, potas s ium acetate, lith ium acetate, calcium
acetate, and th e like. Furth er, th e am ount us ed of th e inorganic
alkali s olution is not particularly lim ited, but th e inorganic
alkali content m ay be us ually in a range of about 0. 1- to
100- f old m oles , pref erably about 0. 5 - to 5 0- f old m oles , per
100 m oles of th e h eteropoly acid us ed. In addition, th e con
centration of th e aq ueous inorganic alkali s olution is not als o
particularly lim ited, but it is us ually about 0. 001 to 5 0%,
pref erably about 0. 01 to 10%.
[ 0073] Th e s tep 3 is a s tep of obtaining an organic s olution
( C) containing th e epoxy com pound af ter contacting th e
organic s olution ( B) obtained in th e s tep ( 2) With an acidic
aq ueous s olution containing a poly m er h av ing at leas t one
f unctional group s elected f rom th e group cons is ting of a
carboxy l group and a s ulf onic acid group ( h ereinaf ter m ay be
s im ply ref erred to as poly m er) ( h ereinaf ter m ay be s im ply
ref erred to as aq ueous poly m er s olution) . Speci? cally , af ter
m ixing th e organic s olution ( B) With th e aq ueous poly m er
s olution, th e res ulting s olution is s eparated into an aq ueous
ph as e and an organic ph as e. Th en, an organic s olution ( C)
containing th e epoxy com pound is obtained by rem ov ing th e
aq ueous ph as e or collecting th e organic ph as e. In th is s tep, th e
contact of th e poly m er With th e q uaternary s alt com pound
contained in th e organic s olution ( B) alloWs an ins oluble s alt
obtained by ads orption of th e q uaternary s alt com pound onto
th e poly m er to precipitate in th e organic ph as e. In addition,
s om e q uaternary s alt com pounds are cons idered to trans f er to
th e aq ueous poly m er s olution, Wh ich is th e aq ueous ph as e.
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Th en, th e q uaternary s alt com pound is rem ov ed f rom th e
organic s olution ( B) by ? ltering of f th e ins oluble s alt or s epa
rating th e aq ueous ph as e.
[ 0074] Exam ples of th e poly m er include poly m ers h av ing a
carboxy l group ( e. g. , poly ( m eth ) acry lic acid, poly m aleic
acid, carboxy m eth y l cellulos e, poly as partic acid, poly
glutam ic acid, poly alginic acid, and poly ( m eth ) acry lic acid/
m aleic acid copoly m ers ) ; poly m ers h av ing a s ulf o group
( e. g. , poly s ty rene s ulf onic acid) ; copoly m ers h av ing both a
carboxy l group and a s ulf o group ( e. g. , poly ( m eth ) acry lic
acid/s ulf onic acid copoly m ers ) ; and m etal s alts th ereof ,
am ong Wh ich poly acry lic acid, poly m aleic acid, poly s ty rene
m aleic acid, poly s ty rene s ulf onic acid, carboxy m eth y l cellu
los e, and alkali m etal s alts th ereof are particularly pref erable,
and poly acry lic acid, poly m aleic acid, and alkali m etal s alts
th ereof are es pecially pref erable. Th e m etals th at f orm a s alt
include alkali m etals ( e. g. , s odium and potas s ium ) ; and alka
line earth m etals ( e. g. , calcium and m agnes ium ) , am ong
Wh ich s odium is particularly pref erable. Furth er, th e neutral
iZ ation ratio of th e poly m er is not particularly lim ited, but it is
us ually about 10 to 9 0%.
[ 0075 ] In addition, th e aq ueous poly m er s olution needs to
be acidic f rom th e v ieWpoint of th e rem ov al e? iciency of th e
q uaternary s alt com pound contained in th e organic s olution
( B) , and th e pH is us ually about 1 to 6, pref erably about 2 to
5 . Th e adj us tm ent of pH can be perf orm ed With th e us e of
acids ( e. g. , s ulf uric acid and h y droch loric acid) or alkalis
( e. g. , s odium h y droxide) .
[ 0076] Als o, th e ph y s ical properties of th e poly m er are not
particularly lim ited, but f rom th e v ieWpoint of th e rem ov al
ef ? ciency of th e q uaternary s alt com pound contained in th e
organic s olution ( B) , th e Weigh t av erage m olecularWeigh t ( in
term s of poly s ty rene as m eas ured by gel perm eation ch rom a
tograph y m eth od. Th e s am e s h all apply h ereinaf ter. ) is us u
ally about 5 00 to 200, 000, pref erably about 1, 000 to 100, 000,
and m ore pref erably 1, 5 00 to 5 5 , 000.
[ 0077] Th e concentration of th e aq ueous poly m er s olution
is not particularly lim ited, but it is us ually about 1 to 20% by
Weigh t f rom th e v ieWpoint of th e rem ov al e? iciency of th e
q uaternary s alt com pound contained in th e organic s olution
( B) .
[ 0078] Th e am ount us ed of th e aq ueous poly m er s olution is
not particularly lim ited, but f rom th e v ieWpoint of th e
rem ov al ef ? ciency of th e q uaternary s alt com pound con
tained in th e organic s olution ( B) , it is us ually 0. 5 - to 5 . 0- f old
Weigh t, pref erably 1- to 2. 5 - f old Weigh t, bas ed on th e Weigh t
of th e q uaternary s alt com pound us ed in th e preparation of th e
organic s olution ( A) .
[ 0079 ] Th e tem perature at th e tim e of contacting th e aq ue
ous poly m er s olution With th e organic s olution ( B) , s peci?
cally th e tem perature of th e m ixture liq uid of th e tWo s olu
tions , is not particularly lim ited, but it is us ually about 0 to
1000 C. , pref erably about 20 to 600 C. , f rom th e v ieWpoint of
th e rem ov al ef ? ciency of th e q uaternary s alt com pound con
tained in th e organic s olution ( B) , liq uid- liq uid extraction
properties , Workability , or th e like. In addition, th e contact
tim e is not als o particularly lim ited, but it is us ually about 1 to
180 m inutes , pref erably about 5 to 60 m inutes , f rom th e
v ieWpoint of th e rem ov al ef ? ciency of th e q uaternary s alt
com pound.
[ 0080] Th e am ount of th e q uaternary s alt com pound con
tained in th e organic s olution ( C) th us obtained is greatly
reduced in com paris on With th at contained in th e organic
Mar. 13, 2014
s olution ( A) . Furth er, th e epoxy com pound obtained f rom th e
organic s olution ( C) h as a h igh purity becaus e th e res idual
content of th e q uaternary s alt com pound contained th erein is
s m all.
[ 0081] Th e purity of th e epoxy com pound contained in th e
organic s olution ( C) can be q uanti? ed by knoWn m eans s uch
as gas ch rom atograph y . Th e am ount of th e q uaternary s alt
com pound contained in th e organic s olution ( C) can als o be
q uanti? ed by a trace nitrogen analy Z er. At th is tim e, it is
pos s ible to us e a calibration curv e prepared f or th e s am e
q uaternary s alt com pound.
[ 0082] Furth er, th e organic s olution ( C) can be f urth er s ub
j ected to knoWn puri? cation m eans as needed, us ing an ads or
bent s uch as activ ated carbon or s ilica, s o th at th e epoxy
com pound h av ing a f urth er im prov ed purity can be obtained.
[ 0083] Th e epoxy com pound obtained by th e production
m eth od of th e pres ent inv ention is a com pound in Wh ich th e
carbon- carbon double bond contained in th e ole? n com pound
is conv erted to a 1, 2- epoxy eth ane s tructure. Als o, f or
exam ple, in th e cas e Wh ere an ole? n com pound containing
tWo carbon- carbon double bonds is us ed as th e s tarting m ate
rial, th e res ulting epoxy com pound m ay be a m ixture of a
m onoepoxy body and a diepoxy body . HoWev er, th e adj us t
m ent of th e am ount us ed of th e oxidiZ ing agent ( aq ueous
h y drogen peroxide s olution, h eteropoly acid) als o m akes it
pos s ible to s electiv ely obtain th e diepoxy body in a large
am ount.
[ 0084] For exam ple, a diepoxy com pound repres ented by
th e f olloWing general f orm ula ( 1' ) can be obtained f rom th e
ole? n com pound repres ented by th e general f orm ula ( 1) .
General f orm ula ( 1' ) :
[ Form ula 9 ]
R7 R8 9 0 R11 R12
R R10
R6 R13
0
o R1 R18 o
s 14
R R2 R17 R
R4 R3 R16 R15
( Wh erein, R1, R2, R3, R4, R5 , R6, R7, R8, R9 , R10, R11, R12,
R13, R14, R15 , R16, R17, and R18 each repres ent a h y drogen
atom or th e s ub s tituent. In addition, m l and m 2 each repres ent
0 or 1. Furth er, Wh en m l is 1, th is m eans th at a m eth y lene
m l is 0, th is m eans th at a m eth y lene group is not pres ent in th e
ring. In addition, Wh en m 2 is 1, th is m eans th at a m eth y lene
m 2 is 0, th is m eans th at a m eth y lene group is not pres ent in th e
ring. HoWev er, Wh en m l is 1, eith er or both of R3 and R4 are
h y drogen, and eith er or both of R7 and R8 are h y drogen. Als o,
Wh en m 2 is 1, eith er or both of R1 1 and R12 are h y drogen, and
eith er or both of R15 and R16 are h y drogen. )
[ 0085 ] In addition, an epoxy com pound repres ented by th e
f olloWing general f orm ula ( 2' ) can be obtained f rom th e ole? n
com pound repres ented by th e general f orm ula ( 2) .
US 2014/0073806 A1
[ Form ula 10]
24 25 O
R R R26
R23 R27
0/
0
R22 R19
R21 R20
( wh erein, R19 , R20, R21, R22, R23, R24, R25 , R26 and R27 each
repres ent a h y drogen atom or th e s ubs tituent. In addition, n
repres ents 0 or 1, and wh en n is 1, th is m eans th at a m eth y lene
group is pres ent in th e cros s linked f orm in th e ring, and wh en
n is 0, th is m eans th at a m eth y lene group is not pres ent in th e
ring. Howev er, wh en n is 1, eith er or both of R20 and R21 are
h y drogen, and eith er or both of R24 and R25 are h y drogen. )
[ 0086] In addition, a diepoxy com pound repres ented by th e
f ollowing general f orm ula ( 3' ) and a m onoepoxy com pound
repres ented by th e f ollowing general f orm ula ( 3" ) can be
obtained f rom th e ole? n com pound repres ented by th e gen
eral f orm ula ( 3) .
[ Form ula 11]
R32 R33 R35 R36
R31 R34 R37
0 0
R30 R39 R38
R29 R28
General f orm ula ( 3" ) :
[ Form ula 12]
R32 R33 R35 R36
R31 R34 R37
0
R30 R39 R38
R29 R28
( wh erein, R28 R29 R30 R31 R32 R33 R34 R35 R36 R37 R38
and R39 each repres ent a h y drogen atom or th e s ubs tituent. In
addition, p repres ents 0 or 1, and wh en p is 1, th is m eans th at
ring, and wh en p is 0, th is m eans th at a m eth y lene group is not
pres ent in th e ring. Howev er, wh en p is 1, eith er or both of R28
h y drogen. )
[ 0087] In addition, an epoxy com pound repres ented by th e
f ollowing general f orm ula ( 4' ) and a m onoepoxy com pound
repres ented by th e f ollowing general f orm ula ( 4" ) can be
obtained f rom th e ole? n com pound repres ented by th e gen
eral f orm ula ( 4) .
Mar. 13, 2014
[ Form ula 13]
R46 R47 R49
0
R45 R48 R5 0
0 R40
44
R R41
R43 R42
General f orm ula ( 4" ) :
[ Form ula 14]
R46 R47 R49
0
R45 R48 R5 0
R40
44
R R41
R43 R42
( wh erein, R40, R41, R42, R43 , R44, R45 , R46, R47, R48, R49 and
R5 0 each repres ent a h y drogen atom or th e s ubs tituent. In
addition, q repres ents 0 or 1, and wh en q is 1, th is m eans th at
ring, and wh en q is 0, th is m eans th at a m eth y lene group is not
pres ent in th e ring. Howev er, wh en q is 1, eith er or both of R42
h y drogen. )
[ 0088] In addition, an epoxy com pound repres ented by th e
f ollowing general f orm ula ( 5 ' ) can be obtained f rom th e ole? n
com pound repres ented by th e general f orm ula ( 5 ) .
General f orm ula ( 5 ' ) :
[ Form ula 15 ]
( wh erein, R5 1, R5 2, R5 3, R5 4, R5 5 , R5 6, R5 7 and R5 8 each
[ 0089 ] In addition, an epoxy com pound repres ented by th e
f ollowing general f orm ula ( 6' ) can be obtained f rom th e ole? n
[ Form ula 16]
R62 R63 R64
R61 R65
0
R60 R66
R5 9
( wh erein, R5 9 , R60, R61, R62, R63, R64, R65 and R66 each
US 2014/0073806 A1
[ 009 0] Speci? c exam ples of th e s ubs tituent in th e general
f orm ulas ( 1' ) , ( 2' ) , ( 3' ) , ( 4' ) , ( 5 ' ) , and ( 6' ) include pref erably
alky l groups With about 1 to 5 carbon atom s am ong th e alky l
groups des cribed abov e, th e polar groups ( e. g. , h alogen and
h y droxy l group) , and th e like.
[ 009 1] In addition, an epoxy com pound in Wh ich th e car
bon- carbon double bond is conv erted to a 1, 2- epoxy eth ane
s tructure can be obtained f rom th e terpene- bas ed ole? n com
pound ( s ee WO 2011/010614) .
[ 009 2] In addition, an epoxy com pound repres ented by th e
f olloWing general f orm ula ( 7' ) can be obtained f rom th e ole? n
[ Form ula 17]
R68 0 R69
( wh erein, R66, R67, R68, and R69 each repres ent a h y drogen
atom or an alky l group With about 3 to 30 carbon atom s ,
pref erably about 6 to 30 carbon atom s ( prov ided th at a
cy cloalky l group is excluded) or an alkeny l group With about
3 to 30 carbon atom s , pref erably about 6 to 30 carbon atom s
( prov ided th at a cy cloalkeny l group is excluded) With th e
prov is o th at th e cas e Wh ere R66, R67, R68, and R69 are all
h y drogen is excluded. Th e num ber of carbon- carbon double
bond( s ) contained in th e alkeny l group is about 1 to 3. In
addition, th e alky l group and th e alkeny l group m ay h av e th e
s ubs tituent ( s ) as des cribed abov e. )
Exam ple
[ 009 3] Th e pres ent inv ention Will be des cribed beloW in
m ore detail by Way of exam ples and com parativ e exam ples ,
but th e inv ention is not intended to be lim ited th ereto.
[ 009 4] In each exam ple, th e term purity is a v alue ( %)
obtained by determ ining th e peak intens ity ( detection v olt
age) of th e epoxy com pound contained in th e organic s olution
( C) and th e total intens ity ( detection v oltage) of all peaks
f rom th e ch art of th e organic s olution ( C) as m eas ured under
th e f olloWing conditions us ing a com m ercially av ailable gas
ch rom atograph y /m as s s pectrom eter ( product nam e 789 OA/
5 9 75 C , m anuf actured by Agilent Tech nologies J apan L td. ) ;
div iding th e f orm er by th e latter; and m ultiply ing th e div ided
v alue by 100.
( Conditions )
[ 009 5 ] Colum n: HP- 5 MS ( m anuf actured by Agilent) 30
m - 0. 25 m m - 0. 25 pm
[ 009 6] Inj ection v olum e: 1 pl, s plit ratio 5 0: 1
[ 009 7] Inj ection tem perature: 300 C.
[ 009 8] D etection tem perature: 300 C.
[ 009 9 ] Ov en: 5 0 C. ( 5 m inutes , retention) l0 C. /m inute
300 C. ( 5 m inutes , retention)
[ 0100] D etector: Hy drogen ? am e ioniZ ation detector
[ 0101] Meas urem ent s am ple: A s am ple ( 0. 1 m L ) taken
f rom th e organic s olution ( C) and diluted With 2 m L of tolu
ene.
[ 0102] In each exam ple, th e rem ov al rate ( %) of th e q ua
ternary s alt com pound ref ers to a v alue obtained f rom th e
expres s ion: [ 1 [ ( res idual am ount ( ppm ) of q uaternary s alt
Mar. 13, 2014
com pound contained in organic s olution ( C) /res idual am ount
( ppm ) of q uaternary s alt com pound contained in organic s olu
tion ( A) ) ] > < 100] . Th e res idual am ount of th e q uaternary s alt
com pound contained in th e organic s olution ( A) or ( C) is a
v alue obtained by m eas urem ent us ing a com m ercially av ail
able trace nitrogen analy Z er ( product nam e TN - 10 , m anu
f actured by Mits ubis h i Ch em ical Corporation) , f olloWed by
determ ination bas ed on a predeterm ined calibration curv e.
Th e calibration curv e ( v ertical axis : nitrogen content; h ori
Z ontal axis : em is s ion intens ity ) h as been prepared f rom a
toluene s olution containing only th e q uaternary s alt com
pound as a s olute.
( Conditions )
[ 0103] Inj ection v olum e: 10 ul
[ 0104] Meas uring range: 5 0 ppm or 1 ppm
[ 0105 ] Furth er, aq ueous poly m er s olutions P1 to P16 us ed
in th e s tep 3 are as f olloWs . Each am ount us ed of th e aq ueous
poly m er s olutions P1 to P16 is 2. 5 - f old Weigh t of th e poly
m er, bas ed on th e Weigh t of th e q uaternary s alt com pound
us ed in th e s tep 1.
[ 0106] P1: An aq ueous s olution obtained by f urth er adj us t
ing a 5 % dilute aq ueous s olution of a com m ercially av ailable
aq ueous poly acry lic acid s olution ( m olecular Weigh t 6, 000,
m anuf actured by Toagos ei Co. , L td. , trade nam e Aron
A- 10SL ) to pH 3 With s ulf uric acid.
ing a 5 % dilute aq ueous s olution of AronA- 10SL to pH 4 With
s ulf uric acid.
ing a 5 % dilute aq ueous s olution of Aron A- 10SL to pH 12
With s odium h y droxide.
[ 0109 ] P4: An aq ueous s olution obtained by f urth er adj us t
ing a 5 % dilute aq ueous s olution of Aron A- 10SL to pH 13
[ 0110] P5 : An aq ueous s olution obtained by f urth er adj us t
ing a 5 % dilute aq ueous s olution of a com m ercially av ailable
aq ueous poly acry lic acid/poly s ty rene s ulf onic acid copoly
m er s olution ( m olecular Weigh t 6, 000, m anuf actured by N IP
PON SHOK UBAI CO. , L TD . , trade nam e Aq ualic GL 366 )
to pH 2 With s ulf uric acid.
ing a 5 % dilute aq ueous s olution of Aq ualic GL 366 to pH 3
With s ulf uric acid.
With s ulf uric acid.
[ 0114] P9 : An aq ueous s olution obtained by f urth er adj us t
[ 0115 ] P10: An aq ueous s olution obtained by f urth er
adj us ting a 5 % dilute aq ueous s olution of a com m ercially
av ailable aq ueous poly acry lic acid s olution ( m olecular
Weigh t 2, 000, m anuf actured by Toagos ei Co. , L td. , trade
nam e Aron A- 210 ) to pH 2 With s ulf uric acid.
[ 0116] P11: An aq ueous s olution obtained by f urth er
adj us ting a 5 % dilute aq ueous s olution of Aron A- 210 to pH
3 With s ulf uric acid.
12 With s odium h y droxide.
US 2014/0073806 A1
13 With s odium h y droxide.
[ 0119 ] P14: An aq ueous s olution obtained by f urth er
adj us ting a 5 % dilute aq ueous s olution of a com m ercially
av ailable aq ueous poly acry lic acid s olution ( m olecular
Weigh t 5 0, 000, m anuf actured by N IPPON SHOK UBAI CO. ,
L TD . , trade nam e Aq ualic D L 45 3 ) to pH 3 With s ulf uric
acid.
[ 0120] P15 : An aq ueous s olution obtained by f urth er
adj us ting a 5 % dilute aq ueous s olution of Aq ualic D L 45 3 to
pH 4 With s ulf uric acid.
adj us ting a 5 % dilute aq ueous s olution of Aq ualic D L 45 3 to
pH 13 With s odium h y droxide.
Exam ple 1
[ 0122] Into a tes t tube eq uipped With a m agnetic s tirrer
Were ch arged 2. 34 g ( 24. 4 m m ol) of a 35 . 5 % ( by Weigh t)
aq ueous h y drogen peroxide s olution, 123 m g ( 0. 24 m m ol) of
m eth y ltriocty l am m onium ch loride, 80 m g ( 0. 24 m m ol) of a
s odium tungs tate dih y drate, and 141 m g ( 0. 6 m m ol) of a
42. 5 % ( by Weigh t) aq ueous ph os ph oric acid s olution, and th e
m ixture Was s tirred at room tem perature f or 30 m inutes to
prepare an aq ueous cataly s t s olution. Th en, 2. 69 g ( 12. 2
m m ol) of a diole? n com pound ( * 1) repres ented by th e f ol
loWing s tructure and 2. 69 g of toluene Were added to th e
aq ueous cataly s t s olution, and th e m ixture Was s ubj ected to
oxidation reaction With s tirring at 5 00 C. f or 10 h ours . Am ong
tWo ph as es s eparated into an aq ueous ph as e and an organic
ph as e af ter th e com pletion of th e reaction, th e organic ph as e
Was s erv ed as an organic s olution ( A) . Th e rem aining am ount
of th e m eth y ltriocty l am m onium ch loride in th e organic s olu
tion ( A) Was 1805 3 ppm .
[ Form ula 18]
< Step 2>
[ 0123] To th e organic s olution ( A) Was added 4. 40 g of a 2%
aq ueous s olution of s odium h y droxide ( N aOH) corres pond
ing to 10 eq uiv alents relativ e to th e s odium tungs tate dih y
drate, and th e m ixture Was s tirred and alloWed to s tand to
s eparate it into tWo ph as es of an aq ueous ph as e and an organic
ph as e, am ong Wh ich th e organic ph as e Was s erv ed as an
organic s olution ( B) .
< Step 3>
[ 0124] To th e organic s olution ( B) Was added 4. 9 0 g of th e
aq ueous poly m er s olution P1 , and th e m ixture Was s tirred and
alloWed to s tand to s eparate it into tWo ph as es of an aq ueous
ph as e and an organic ph as e, am ong Wh ich th e organic ph as e
Was s erv ed as an organic s olution ( C) containing a diepoxy
com pound ( * * 1) repres ented by th e f olloWing s tructure. Th e
Mar. 13, 2014
purity of th e diepoxy com pound, and th e res idual am ount and
rem ov al rate of th e q uaternary s alt com pound are s h oWn in
Table 1.
[ Form ula 19 ]
Exam ple 2
[ 0125 ] An organic s olution ( C) containing th e diepoxy
com pound ( * * 1) Was obtained in th e s am e m anner as in
Exam ple 1 except th at th e aq ueous poly m er s olution P1 ( 4. 9 0
g) us ed in th e s tep 3 Was replaced by th e aq ueous poly m er
s olution P6 ( 4. 9 0 g) . Th e res ults are s h oWn in Table 1.
Exam ple 3
[ 0126] An organic s olution ( C) containing th e diepoxy
Exam ple 4
Exam ple 1 except th at th e m eth y ltriocty l am m onium ch loride
( 123 m g, 0. 24 m m ol) us ed in th e s tep 1 Was replaced by
dialky ldim eth y l am m onium ch loride ( a m ixture of C8 to C18
alky l ch ains ) ( 146 m g, 0. 24 m m ol) . Th e res ults are s h oWn in
Table 1.
Exam ple 5
didecy ldim eth y l am m onium ch loride ( 146 m g, 0. 24 m m ol) .
Th e res ults are s h oWn in Table 1.
Exam ple 6
didecy ldim eth y l am m onium ch loride ( 110 m g, 0. 24 m m ol)
and th e aq ueous poly m er s olution P1 ( 4. 9 0) us ed in th e s tep 3
Was replaced by th e aq ueous poly m er s olution P6 ( 4. 00 g) .
Com parativ e Exam ple 1
Exam ple 1 except th at th e s tep 2 Was om itted and th e organic
s olution ( A) obtained in th e s tep 1 Was regarded as th e organic
s olution ( B) . Th e res ults are s h oWn in Table 1.
US 2014/0073806 A1
Exam ple 1 except th at th e s tep 3 Was om itted. In th is com
parativ e exam ple, th e organic s olution ( B) obtained in th e s tep
2 Was regarded as th e organic s olution ( C) . Th e res ults are
s h oWn in Table 1.
and th e s tep 2 Was om itted. In th is com parativ e exam ple, th e
organic s olution ( A) obtained in th e s tep 1 Was regarded as th e
organic s olution ( B) . Th e res ults are s h oWn in Table 1.
Exam ple Com parativ e Exam ple 5
and th e aq ueous poly m er s olution P1 ( 4. 9 0 g) us ed in th e s tep
3 Was replaced by th e aq ueous poly m er s olution P4 ( 4. 00 g) .
11
Mar. 13, 2014
[ 0135 ] In Table 1, WA- N a repres ents s odium tungs tate
dih y drate and PA repres ents ph os ph oric acid, res pectiv ely
( th e s am e s h all apply to Tables 2 to 7) .
Exam ple 7
< Step 1>
aq ueous h y drogen peroxide s olution, 0. 48 g ( 0. 81 m m ol) of
dialky ldim eth y l am m onium ch loride ( a m ixture of C8 to C18
alky l ch ains ) , 0. 27 g ( 0. 81 m m ol) of a s odium tungs tate dih y
drate, and 0. 46 g ( 2. 01 m m ol) of a 42. 5 % ( by Weigh t) aq ueous
ph os ph oric acid s olution, and th e m ixture Was s tirred at room
tem perature f or 30 m inutes to prepare an aq ueous cataly s t
s olution. Th en, 5 . 00 g ( 40. 3 m m ol) of a m onoole? n com
pound ( * 2) repres ented by th e f olloWing s tructure and 5 . 00 g
of toluene Were added to th e aq ueous cataly s t s olution, and
th e m ixture Was s ubj ected to oxidation reaction With s tirring
at 5 00 C. f or 10 h ours . Am ong tWo ph as es s eparated into an
aq ueous ph as e and an organic ph as e af ter th e com pletion of
th e reaction, th e organic ph as e Was s erv ed as an organic
s olution ( A) . Th e rem aining am ount of th e dialky ldim eth y l
am m onium ch loride in th e organic s olution ( A) Was 18721
[ Form ula 20]
OH
TABL E 1
Step 3
Organic s olution C
Step 1 Step 2 Quaternary
Organic s olution ( A) In- s alt com pound
Hetero Quaternary organic Aq ueous Epoxy Re
Is opoly atom s alt com pound alkali poly m er s olution com pound m ov al
Ole? n acid donor K ind ppm s olution Sy m bol K ind Mn pH K ind Purity ppm rate
Exam ple 1 * 1 WA- N a PA ( Oct) 3MeN * Cl 1805 3 N aOH P1 A- 10SL 6000 3 * * 1 9 8% 109 3 9 3 . 9
Exam ple 2 * 1 WA- N a PA ( Oct) 3MeN * Cl 1805 3 N aOH P6 GL 366 6000 3 * * 1 9 8% 3366 81. 4
Exam ple 3 * 1 WA- N a PA ( Oct) 3MeN + Cl 1805 3 N aOH P10 A- 210 2000 2 * * 1 9 8% 4675 74. 1
Exam ple 4 * 1 WA- N a PA R2( Me) 2N + Cl ( R = 20 63 8 N aOH P1 A- 10SL 6000 3 * * 1 9 8% 9 29 9 5 . 5
C8- 18)
Exam ple 5 * 1 WA- N a PA ( D ecy l) 2( Me) 2N * Cl 9 5 64 N aOH P1 A- 10SL 6000 3 * * 1 9 8% 437 9 5 . 4
Exam ple 6 * 1 WA- N a PA ( D ecy l) 2( Me) 2N + Cl 9 5 64 N aOH P6 GL 366 6000 3 * * 1 9 8% 1233 87. 1
Com parativ e * 1 WA- N a PA ( Oct) 3MeN * Cl 1805 3 i P1 A- 10SL 6000 3 * * 1 9 8% 139 03 23 . 0
Exam ple 1
Com parativ e * 1 WA- N a PA ( Oct) 3MeN * Cl 1805 3 N aOH P4 A- 10SL 6000 13 * * 1 9 6% 18002 0. 3
Exam ple 2
Com parativ e * 1 WA- N a PA ( Oct) 3MeN * Cl 1805 3 N aOH i * * 1 9 6% 179 9 5 0. 3
Exam ple 3
Com parativ e * 1 WA- N a PA ( D ecy l) 2( Me) 2N + Cl 9 5 64 i P1 A- 10SL 6000 3 * * 1 9 6% 9 35 2 2. 2
Exam ple 4
Com parativ e * 1 WA- N a PA ( D ecy l) 2( Me) 2N * Cl 9 5 64 N aOH P4 A- 10SL 6000 13 * * 1 9 6% 9 411 1. 6
Exam ple 5
US 2014/0073806 A1
< Step 3>
[ 0138] To th e organic s olution ( B) Was added 19 . 2 g of th e
Was s erv ed as an organic s olution ( C) containing a m onoep
oxy com pound ( * * 2) repres ented by th e f ollowing s tructure.
Th e purity of th e m onoepoxy com pound, and th e res idual
am ount and rem ov al rate of th e q uaternary s alt com pound are
s h oWn in Table 2.
[ Form ula 21]
OH
Exam ple 8
[ 0139 ] An organic s olution ( C) containing th e m onoepoxy
Exam ple 7 except th at th e aq ueous poly m er s olution P1 ( 19 . 2
s olution P6 ( 19 . 2 g) . Th e res ults are s h oWn in Table 2.
[ 0140] An organic s olution ( C) containing th e m onoepoxy
s h oWn in Table 2.
g) Was replaced by th e aq ueous poly m er s olution P4 ( 19 . 2 g) .
Mar. 13, 2014
Exam ple 9
Were ch arged 9 . 06 g ( 9 4. 5 m m ol) of a 35 . 5 % ( by Weigh t)
m eth y ltriocty l am m onium ch loride, 0. 12 g ( 0. 38 m m ol) of a
s odium tungs tate dih y drate, and 0. 22 g ( 0. 9 5 m m ol) of a
prepare an aq ueous cataly s t s olution. Th en, 5 . 00 g ( 37. 8
m m ol) of a diole? n com pound ( * 3) repres ented by th e f ol
loWing s tructure and 5 . 00 g of toluene Were added to th e
oxidation reaction With s tirring at 5 00 C. f or 10 h ours . Am ong
tWo ph as es s eparated into an aq ueous ph as e and an organic
ph as e af ter th e com pletion of th e reaction, th e organic ph as e
Was s erv ed as an organic s olution ( A) . Th e rem aining am ount
of th e m eth y ltriocty l am m onium ch loride in th e organic s olu
tion ( A) Was 20272 ppm .
[ Form ula 22]
< Step 3>
[ 0144] To th e organic s olution ( B) Was added 7. 70 g of th e
TABL E 2
Step 3
Step 1 Step 2 Organic s olution C
Org_ anic s olution ( A) In- Quaternary
Hetero organic Epoxy s alt com pound
Is opoly atom Quaternag s alt com pound alkali Aq ueous poly m er s olution com pound Rem ov al
Ole? n acid donor K ind ppm s olution Sy m bol K ind Mn pH K ind Purity ppm rate
Exam ple 7 * 2 WA- N a PA R2( Me) 2N * Cl ( R = 18721 N aOH P1 A- 10SL 6000 3 * * 2 9 9 % 4819 74. 3
C8- 18)
Exam ple 8 * 2 WA- N a PA R2( Me) 2N + Cl ( R = 18721 N aOH P6 GL 366 6000 3 * * 2 9 9 % 5 178 72. 3
C8- 18)
Com - * 2 WA- N a PA R2( Me) 2N * Cl ( R = 18721 N aOH i * * 2 9 5 % 18032 3. 7
parativ e C8- 18)
Exam ple 6
Com - * 2 WA- N a PA R2( Me) 2N * Cl ( R = 18721 N aOH P4 A- 10SL 6000 13 * * 2 9 5 % 165 9 8 11. 3
parativ e C8- 18)
Exam ple 7
US 2014/0073806 A1
allowed to s tand to s eparate it into tWo ph as es of an aq ueous
Was s erv ed as an organic s olution ( C) containing a diepoxy
com pound ( * * 3) repres ented by th e f ollowing s tructure. Th e
purity of th e diepoxy com pound, and th e res idual am ount and
Table 3.
[ Form ula 23]
Exam ple 10
Exam ple 9 except th at th e aq ueous poly m er s olution P1 ( 7. 70
s olution P6 ( 7. 70 g) . Th e res ults are s h oWn in Table 3.
Exam ple 11
( 0. 19 g, 0. 38 m m ol) us ed in th e s tep 1 Was replaced by
didecy ldim eth y l am m onium ch loride ( 0. 17 g, 0. 38 m m ol)
and th e aq ueous poly m er s olution P1 ( 7. 70 g) us ed in th e s tep
3 Was replaced by th e aq ueous poly m er s olution P10 ( 6. 9 0 g) .
Exam ple 12
s h oWn in Table 3.
Exam ple 9 except th at th e aq ueous poly m er s olution P1 ( 7. 70
s olution P4 ( 7. 70 g) . Th e res ults are s h oWn in Table 3.
[ 015 0] An organic s olution ( C) containing th e diepoxy
Mar. 13, 2014
and th e s tep 2 Was om itted. In th is com parativ e exam ple, th e
organic s olution ( A) obtained in th e s tep 1 Was regarded as th e
organic s olution ( B) . Th e res ults are s h oWn in Table 3.
Exam ple 13
[ 015 4] Into a tes t tube eq uipped With a m agnetic s tirrer
Were ch arged 7. 9 7 g ( 83. 2 m m ol) of a 35 . 5 % ( by Weigh t)
s odium tungs tate dih y drate, and 0. 19 g ( 0. 83 m m ol) of a
prepare an aq ueous cataly s t s olution. Th en, 5 . 00 g ( 33. 3
m m ol) of a m onoole? n com pound ( * 4) repres ented by th e
f olloWing s tructure and 2. 34 g of toluene Were added to th e
oxidation reaction With s tirring at 5 00 C. f or 10 h ours . Th e
m onoole? n com pound is a m ixture of a com pound Wh erein a
h y droxy l group is bonded to th e 5 - pos ition of th e norbom ane
ring and a com pound Wh erein a h y droxy group is bonded to
th e 6- pos ition of th e norbom ane ring. Am ong tWo ph as es
s eparated into an aq ueous ph as e and an organic ph as e af ter
th e com pletion of th e reaction, th e organic ph as e Was s erv ed
as an organic s olution ( A) . Th e rem aining am ount of th e
m eth y ltriocty l am m onium ch loride in th e organic s olution
( A) Was 23083 ppm .
US 2014/0073806 A1
[ Form ula 24]
< Step 2>
[ 015 5 ] To th e organic s olution ( A) Was added 6. 70 g of a 2%
< Step 3>
[ 015 6] To th e organic s olution ( B) Was added 6. 70 g of th e
oxy com pound ( * * 4) repres ented by th e f ollowing s tructure.
Th e m onoepoxy com pound is a m ixture of a com pound
Wh erein a h y droxy l group is bonded to th e 5 - pos ition of th e
norbornane ring and a com pound Wh erein a h y droxy group is
bonded to th e 6- pos ition of th e norbom ane ring. Th e purity of
th e m onoepoxy com pound, and th e res idual am ount and
Table 3.
Mar. 13, 2014
14
[ Form ula 25 ]
HO O
Exam ple 14
[ 015 7] An organic s olution ( C) containing th e m onoepoxy
Exam ple 13 except th at th e aq ueous poly m er s olution P1
( 6. 70 g) us ed in th e s tep 3 Was replaced by th e aq ueous
poly m er s olution P6 ( 6. 70 g) . Th e res ults are s h oWn in Table
3.
s h oWn in Table 3.
[ 015 9 ] An organic s olution ( C) containing th e m onoepoxy
3.
TAB L E 3
Step 3
Organic s olution ( A) In- Epoxy Quaternary
Hetero organic com pound s alt com pound
Is opoly atom Ouatem ary s alt com pound alkali Aq ueous poly m er s olution Pu- Rem ov al
Ole? n acid donor K ind ppm s olution Sy m bol K ind Mn pH K ind rity ppm rate
Exam ple 9 * 3 WA- N a PA ( Oct) 3MeN + Cl 20272 N aOH P1 A- 10SL 6000 3 * * 3 9 9 % 6619 67. 3
Exam ple 10 * 3 WA- N a PA ( Oct) 3MeN * Cl 20272 N aOH P6 GL 366 6000 3 * * 3 9 9 % 6619 67. 3
Exam ple 11 * 3 WA- N a PA ( D ecy l) 2( Me) 2N * Cl 12806 N aOH P10 A- 210 2000 2 * * 3 9 9 % 5 43 9 5 . 8
Exam ple 12 * 3 WA- N a PA ( D ecy l) 2( Me) 2N + Cl 12806 N aOH P5 GL 366 6000 2 * * 3 9 9 % 875 9 3. 2
Com parativ e * 3 WA- N a PA ( Oct) 3MeN * Cl 20272 N aOH i * * 3 9 7% 2019 1 0. 4
Exam ple 8
Com parativ e * 3 WA- N a PA ( Oct) 3MeN + Cl 20272 N aOH P4 A- 10SL 6000 13 * * 3 9 7% 20002 1. 3
Exam ple 9
Com parativ e * 3 WA- N a PA ( D ecy l) 2( Me) 2N * Cl 12806 N aOH P12 A- 210 2000 12 * * 3 9 7% 119 17 6. 9
Exam ple 10
Com parativ e * 3 WA- N a PA ( D ecy l) 2( Me) 2N * Cl 12806 N aOH P8 GL 3 66 6000 12 * * 3 9 7% 1209 9 5 . 5
Exam ple 11
Com parativ e * 3 WA- N a PA ( D ecy l) 2( Me) 2N + Cl 12806 N aOH P4 A- 10SL 6000 13 * * 3 9 7% 12748 0. 5
Exam ple 12
Com parativ e * 3 WA- N a PA ( D ecy l) 2( Me) 2N * Cl 12806 i P1 A- 10SL 6000 3 * * 3 9 7% 12477 2. 6
Exam ple 13
Exam ple 13 * 4 WA- N a PA ( Oct) 3MeN * Cl 23083 N aOH P1 A- 10SL 6000 3 * * 4 9 9 % 45 30 80. 4
Exam ple 14 * 4 WA- N a PA ( Oct) 3MeN * Cl 23083 N aOH P6 GL 3 66 6000 3 * * 4 9 9 % 45 30 80. 4
Com parativ e * 4 WA- N a PA ( Oct) 3MeN + Cl 230 83 N aOH i * * 4 9 6% 23 0 83 0
Exam ple 14
Com parativ e * 4 WA- N a PA ( Oct) 3MeN * Cl 23083 N aOH P4 A- 10SL 6000 13 * * 4 9 6% 20837 9 . 7
Exam ple 15
US 2014/0073806 A1
Exam ple 15
aq ueous h y drogen peroxide s olution, 0. 49 g ( 0. 9 6 m m ol) of
m eth y ltriocty l am m onium ch loride, 0. 32 g ( 0. 9 6 m m ol) of a
s odium tungs tate dih y drate, 0. 5 5 g ( 2. 40 m m ol) of a 42. 5 %
( by Weigh t) aq ueous ph os ph oric acid s olution, and 2. 04 g
( 14. 4 m m ol) of s odium s ulf ate, and th e m ixture Was s tirred at
room tem perature f or 30 m inutes to prepare an aq ueous cata
ly s t s olution. Th en, 5 . 00 g ( 48. 0 m m ol) of a m onoole? n
com pound ( * 5 ) repres ented by th e f olloWing s tructure and
5 . 00 g of toluene Were added to th e aq ueous cataly s t s olution,
and th e m ixture Was s ubj ected to oxidation reaction With
s tirring at 5 00 C. f or 10 h ours . Am ong tWo ph as es s eparated
into an aq ueous ph as e and an organic ph as e af ter th e com ple
tion of th e reaction, th e organic ph as e Was s erv ed as an
organic s olution ( A) . Th e rem aining am ount of th e m eth y lt
riocty l am m onium ch loride in th e organic s olution ( A) Was
35 421 ppm .
[ Form ula 26]
< Step 2>
[ 0161] To th e organic s olution ( A) Was added 19 . 2 g of a 2%
< Step 3>
aq ueous poly m er s olution P2, and th e m ixture Was s tirred and
oxy com pound ( * * 5 ) repres ented by th e f olloWing s tructure.
s h oWn in Table 4.
[ Form ula 27]
Exam ple 16
com pound ( * * 5 ) Was obtained in th e s am e m anner as in
Mar. 13, 2014
( 19 . 4 g) us ed in th e s tep 3 Was replaced by th e aq ueous
poly m er s olution P7 ( 19 . 4 g) . Th e res ults are s h oWn in Table
4.
s h oWn in Table 4.
( 19 . 4 g) us ed in th e s tep 3 Was replaced by th e aq ueous
poly m er s olution P4 ( 19 . 4 g) . Th e res ults are s h oWn in Table
4.
Exam ple 17
Were ch arged 3. 9 2 g ( 40. 9 m m ol) of a 35 . 5 % ( by Weigh t)
s odium tungs tate dih y drate, 0. 47 g ( 2. 05 m m ol) of a 42. 5 %
( 12. 3 m m ol) of a s odium s ulf ate, and th e m ixture Was s tirred
at room tem perature f or 30 m inutes to prepare an aq ueous
cataly s t s olution. Th en, 5 . 00 g ( 40. 9 m m ol) of a m onoole? n
com pound ( * 6) repres ented by th e f olloWing s tructure and
organic s olution ( A) . Th e rem aining am ount of th e m eth y lt
riocty l am m onium ch loride in th e organic s olution ( A) Was
31684 ppm .
[ Form ula 28]
< Step 2>
< Step 3>
aq ueous poly m er s olution P11, and th e m ixture Was s tirred
US 2014/0073806 A1
and allowed to s tand to s eparate it into tWo ph as es of an
aq ueous ph as e and an organic ph as e, am ong Wh ich th e
organic ph as e Was s erv ed as an organic s olution ( C) contain
ing a m onoepoxy com pound ( * * 6) repres ented by th e f olloW
ing s tructure. Th e purity of th e m onoepoxy com pound, and
th e res idual am ount and rem ov al rate of th e q uaternary s alt
com pound are s h oWn in Table 4.
[ Form ula 29 ]
Exam ple 18
4.
s h oWn in Table 4.
Exam ple 19
4.
Exam ple 19
dialky ldim eth y lam m onium ch loride ( a m ixture of C8 to C18
alky l ch ains ) , 0. 23 g ( 0. 72 m m ol) of a s odium tungs tate dih y
drate, 0. 41 g ( 1. 80 m m ol) of a 42. 5 % ( by Weigh t) aq ueous
ph os ph oric acid s olution, and 1. 5 3 g ( 10. 8 m m ol) of a s odium
s ulf ate, and th e m ixture Was s tirred at room tem perature f or
30 m inutes to prepare an aq ueous cataly s t s olution. Th en,
5 . 00 g ( 36. 1 m m ol) of a m onoole? n com pound ( * 7) repre
s ented by th e f olloWing s tructure and 5 . 00 g of toluene Were
added to th e aq ueous cataly s t s olution, and th e m ixture Was
s ubj ected to oxidation reaction With s tirring at 5 00 C. f or 10
h ours . Am ong tWo ph as es s eparated into an aq ueous ph as e
and an organic ph as e af ter th e com pletion of th e reaction, th e
organic ph as e Was s erv ed as an organic s olution ( A) . Th e
rem aining am ount of th e dialky ldim eth y l am m onium ch lo
ride in th e organic s olution
Mar. 13, 2014
[ Form ula 30]
Cl
oxy com pound ( * * 7) repres ented by th e f olloWing s tructure.
An organic s olution ( C) containing a m onoepoxy com pound
( * * 7) repres ented by th e f olloWing s tructure. Th e purity of th e
m onoepoxy com pound, and th e res idual am ount and rem ov al
rate of th e q uaternary s alt com pound are s h oWn in Table 4.
[ Form ula 31]
Cl
Exam ple 20
4.
s h oWn in Table 4.
4.
US 2014/0073806 A1
Exam ple 19 except th at th e s tep 2 Was om itted and th e aq ue
ous poly m er s olution P1 ( 16. 1 g) us ed in th e s tep 3 Was
replaced by th e aq ueous poly m er s olution P6 ( 16. 1 g) . In th is
com parativ e exam ple, th e organic s olution ( A) obtained in th e
s tep 2 Was regarded as th e organic s olution ( B) . Th e res ults are
s h oWn in Table 4.
Exam ple 21
[ 0179 ] Into a tes t tube eq uipped With a m agnetic s tirrer
aq ueous h y drogen peroxide s olution, 0. 25 m g ( 0. 5 5 m m ol) of
didecy ldim eth y l am m onium ch loride, 0. 18 g ( 0. 5 5 m m ol) of
a s odium tungs tate dih y drate, 0. 31 g ( 1. 37 m m ol) of a 42. 5 %
ly s t s olution. Th en, 5 . 00 g ( 27. 3 m m ol) of a m onoole? n
com pound ( * 8) repres ented by th e f olloWing s tructure and
organic s olution ( A) . Th e rem aining am ount of th e didecy l
dim eth y lam m onium ch loride in th e organic s olution ( A) Was
22489 ppm .
[ Form ula 32]
Br
< Step 3>
oxy com pound ( * * 8) repres ented by th e f olloWing s tructure.
s h oWn in Table 4.
Mar. 13, 2014
[ Form ula 33]
Exam ple 22
s h oWn in Table 4.
Exam ple 23
[ 0185 ] Into a tes t tube eq uipped With a m agnetic s tirrer
ly s t s olution. Th en, 5 . 00 g ( 42. 3 m m ol) of a ole? n com pound
( * 9 ) repres ented by th e f olloWing s tructure and 2. 69 g of
toluene Were added to th e aq ueous cataly s t s olution, and th e
m ixture Was s ubj ected to oxidation reaction With s tirring at
5 00 C. f or 10 h ours . Am ong tWo ph as es s eparated into an
s olution ( A) . Th e rem aining am ount of th e m eth y ltriocty l
am m onium ch loride in th e organic s olution ( A) Was 309 84
[ Form ula 34]
US 2014/0073806 A1
< Step 3>
oxy com pound ( * * 9 ) repres ented by th e f olloWing s tructure.
s h oWn in Table 4.
[ Form ula 35 ]
O
Exam ple 24
4.
s h oWn in Table 4.
4.
Exam ple 25
[ 019 1] Into a tes t tube eq uipped With a m agnetic s tirrer
Mar. 13, 2014
ly s t s olution. Th en, 5 . 00 g ( 42. 3 m m ol) of a diole? n com
pound ( * 10) repres ented by th e f olloWing s tructure and 5 . 00
g of toluene Were added to th e aq ueous cataly s t s olution, and
th e m ixture Was s ubj ected to oxidation reaction With s tirring
[ Form ula 3 6]
< Step 2>
[ 019 2] To th e organic s olution ( A) Was added 16. 9 g of a 2%
< Step 3>
[ 019 3] To th e organic s olution ( B) Was added 17. 1 g of th e
aq ueous poly m er s olution P10, and th e m ixture Was s tirred
and alloWed to s tand to s eparate it into tWo ph as es of an
aq ueous ph as e and an organic ph as e, am ong Wh ich th e
organic ph as e Was s erv ed as an organic s olution ( C) contain
ing a m onoepoxy com pound ( * * 10) repres ented by th e f ol
loWing s tructure. Th e purity of th e m onoepoxy com pound,
and th e res idual am ount and rem ov al rate of th e q uaternary
s alt com pound are s h oWn in Table 4.
[ Form ula 37]
Exam ple 26
4.
[ 019 5 ] An organic s olution ( C) containing th e m onoepoxy
s h oWn in Table 4.
US 2014/0073806 A1
4.
19
Mar. 13, 2014
TABL E 4
Step 3
Org_ anic s olution ( A) In- Epoxy Quaternary
Hetero organic com pound s alt com pound
Is opoly atom Quaternag s alt com pound alkali Agueous poly m er s olution Pu- Rem ov al
Ole? n acid donor K ind ppm s olution Sy m bol K ind Mn pH K ind rity ppm rate
Exam ple 15 * 5 WA- N a PA ( Oct) 3MeN + Cl 35 421 N aOH P2 A- 10SL 6000 4 * * 5 85 % 5 348 84. 9
Exam ple 16 * 5 WA- N a PA ( Oct) 3MeN + Cl7 35 421 N aOH P7 GL 366 6000 4 * * 5 85 % 75 5 8 78. 7
Com parativ e * 5 WA- N a PA ( Oct) 3MeN + Cl 35 421 N aOH i * * 5 83% 34785 1. 8
Exam ple 16
Com parativ e * 5 WA- N a PA ( Oct) 3MeN + Cl7 35 421 N aOH P4 A- 10SL 6000 13 * * 5 83% 33471 5 . 5
Exam ple 17
Exam ple 17 * 6 WA- N a PA ( Oct) 3MeN + Cl 31684 N aOH P11 A- 210 2000 3 * * 6 74% 2419 9 2. 4
Exam ple 18 * 6 WA- N a PA ( Oct) 3MeN + Cl 31684 N aOH P6 GL 366 6000 3 * * 6 74% 4711 85 . 1
Com parativ e * 6 WA- N a PA ( Oct) 3MeN + Cl7 31684 N aOH i * * 6 70% 309 9 4 2. 2
Exam ple 18
Com parativ e * 6 WA- N a PA ( Oct) 3MeN + Cl 31684 N aOH P13 A- 210 2000 13 * * 6 70% 315 74 0. 3
Exam ple 19
Exam ple 19 * 7 WA- N a PA R2( Me) 2N + Cl7( R = 27441 N aOH P1 A- 10SL 6000 3 * * 7 88% 2116 9 2. 3
0818)
Exam ple 20 * 7 WA- N a PA R2( Me) 2N + Cl ( R = 27441 N aOH P6 GL 366 6000 3 * * 7 88% 29 5 4 89 . 2
0818)
Com parativ e * 7 WA- N a PA R2( Me) 2N * c17( R = 27441 N aOH 4 * * 7 86% 2615 7 4. 7
Exam ple 20 C8- 18)
Com parativ e * 7 WA- N a PA R2( Me) 2N + Cl ( R = 27441 N aOH P4 A- 10SL 6000 13 * * 7 86% 25 179 8. 2
Exam ple 21 C8- 18)
Com parativ e * 7 WA- N a PA R2( Me) 2N + Cl7( R = 27441 i P6 GL 366 6000 3 * * 7 86% 2735 8 0. 3
Exam ple 22 C8- 18)
Exam ple 21 * 8 WA- N a PA ( D ecy l) 2( Me) 2N * Cl 22489 N aOH P1 A- 10s L 6000 3 * * 8 81% 45 13 79 . 9
Exam ple 22 * 8 WA- N a PA ( D ecy l) 2( Me) 2N + Cl 22489 N aOH P6 GL 366 6000 3 * * 8 81% 5 9 46 73. 6
Com parativ e * 8 WA- N a PA ( D ecy l) 2 ( Me) 2N + Cl 22489 N aOH i * * 8 7 8% 215 9 8 4. 0
Exam ple 23
Com parativ e * 8 WA- N a PA ( D ecy l) 2( Me) 2N * Cl 22489 N aOH P4 A- 10s L 6000 13 * * 8 78% 20147 10. 4
Exam ple 24
Exam ple 23 * 9 WA- N a PA ( Oct) 3MeN + Cl7 309 84 N aOH P1 A- 10SL 6000 3 * * 9 9 6% 15 49 9 5 . 0
Exam ple 24 * 9 WA- N a PA ( Oct) 3MeN + Cl 309 84 N aOH P6 GL 366 6000 3 * * 9 9 6% 349 8 88. 7
Com parativ e * 9 WA- N a PA ( Oct) 3MeN + Cl 309 84 N aOH i * * 9 9 2% 289 34 6. 6
Exam ple 25
Com parativ e * 9 WA- N a PA ( Oct) 3MeN + Cl7 309 84 N aOH P4 A- 10SL 6000 13 * * 9 9 2% 29 478 4. 9
Exam ple 26
Exam ple 25 * 10 WA- N a PA ( Oct) 3MeN + Cl 30475 N aOH P10 A- 210 2000 2 * * 10 9 9 % 315 9 89 . 6
Exam ple 26 * 10 WA- N a PA ( Oct) 3MeN + Cl7 30475 N aOH P5 GL 366 6000 2 * * 10 9 9 % 45 19 85 . 2
Com parativ e * 10 WA- N a PA ( Oct) 3MeN + Cl7 30475 N aOH i * * 10 9 5 % 28364 6. 9
Exam ple 27
Com parativ e * 10 WA- N a PA ( Oct) 3MeN + Cl 30475 N aOH P9 GL 366 6000 13 * * 10 9 5 % 27369 10. 2
Exam ple 28
Exam ple 27 room tem perature f or 30 m inutes to prepare an aq ueous cata
ly s t s olution. Th en, 5 . 00 g ( 37. 8 m m ol) of a diole? n com
< Step 1> pound ( * 11) repres ented by th e f ollowing s tructure and 5 . 00
g of toluene Were added to th e aq ueous cataly s t s olution, and
[ 019 7] Into a tes t tube eq ulpped Wlth a m agnetlc s tlrrer th e m ixture Was s ubj ected to oxidation reaction With s tirring

United States: (12) Patent Application Publication (10) Pub. No.: US 2014/0073806 A1

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United States: (12) Patent Application Publication (10) Pub. No.: US 2014/0073806 A1

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US 20140073 806A1

( 12) Patent Application Publication ( 10) Pub. N o. : US 2014/0073806 A1

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