le
[45]
[54]
ET OD EP RI S·NIT S·NITROF ROFURF URFURA URA DIACET DIACETATE ATE
[76]
Inve Invent ntor ors: s:
OTHE OTHE
Solo Solomo mo Aron Aronov ovic ic Gill Giller er ulit ulitsa sa Pernavas, 10 kv 76 Karl Karl Karl Karlov ovic ic er ts Sp a, 10 Marg Margar arit it Aldo Aldono noma ma Trus Trushu hule le ulit ulitsa sa Katr Katrin inda damb mbis is 22-0 22-0 kv 10 Gunt Guntis is Erik Erikovi ovich ch Bergg Berggrin rin ulit ulitsa sa Perna Pernava vas, s, 57 kv 10 Robe Robert rt Avgu Avgust stov ovic ic Brin Brinkm kman anis is ulit ulitsa sa Briv Brivze zemn mnie ieka ka 22 kv. 4, al of Riga Riga Vldi Vldi Yano Yanovi vich ch Mikst Mikstai ais, s, uJit uJitsa sa Elgav Elgavas, as, 4, kv. 64 Paul Paul Alexa Alexandr ndrov ovich ich Stank Stankevi evich ch ulits ulits
PUBL PUBLIC ICAT ATIO IONS NS
c. (1959), pp 746746-74 748. 8. R. Jile Jile Primary Primary Examiner Examiner-Hen -Henry ry Dentz Assistan Assistan Examine Examiner-Be r-Bernar rnar Jacobson Atto Attorn rney ey Agen Agent. t. or Firm Firm-F -F1e 1eit it ABSTRACI'
[57J ho
hu
Olai Olaine ne al of U.S. U.S.S. S.R. R.
ar
·n
ds n.
et
ir
Ma [51] (S2J
4,052,419
[11]
rJ91
Int. CI.2 U.S. Ct
ra
yd
io
1:1. 1:1.11-2: 2:0. 0.03 0366-0. 0.04 04
27,1 27,197 97
fu
ix
ce
hi
pe ur 10°C 10°C unde unde cont contin in e. do so ar
resp respec ecti tive vely ly an
said said comp compou ound nd
C07D 307nl 260/347.4
260/347.4
ra
ed wi
te
ht ra
we
1.1:1 to 1.8:1 [56)
Refer Referen ences ces Cite Cite AT
OC ME TS
mp 260/347.4
Unit United ed King Kingdom dom
260/347.4 260/347.4
tu
desi desire re mixture.
it
th
to 25· C, main main to 55 prod produc uc is ther therea eaft fter er isol isolat ated ed from from said said reac reacti tion on Clai Claims ms
an
45
Draw Drawin in Figu Figure re
u.s.
Patent
4,052,419
4,052,419 ME HO
REPARING ·NITROFURF RA DlACETATE
Amount of th starting nitric lCid in mixtur with acetic anhydride, per cent
Th re en in ntio relate to meth pr pari S-nitrofurfunl diacetat by nitratio of furfural or furfuNitr ur ur whic
ia tate isa st rtin
ra
at ri
it
rf
ta
rf
does no detonate
41 50
th
find an extensiv us in medicine an agriculture.
Properties of th prepared solution of lCetyl nitrat in acetic anhydride
detonates
lIO
70
10
rf
ly
il te
r~
ti an mcreased xp nsiv ce
10
meth ds on is
ty
th
ra
ll wing teps
is
(CH)COhQ
co sumpti
gr at mounts
rather
-to·
HNO)
thereo is substantiall
CH)COON0
impaired This ma be attributed
CH1COOH
:a dride to te (a). he mtrati effected at temperatur 2t and .S
is decreased while concentratio
10
'!
~u.r furf ra ia et te Within th rang .o fn;>
ti
in
it ic
re imin ry ri in
tu
tr
.e
mtric
35 in inac ti
nhydri
isshow inTa le
rein low.
S'
, a ntammg an Interm iate nttr on
ro uc
it
(b)
?l
d ( centrate SUlphuri acid (specifi gravit 1.84 an ace40 ti hydrid er 1:1.3:0.036:6.S respectively).
I.S:1 respecO·
th
to th
ra
ro
re
upon cooling.
8to
·to
tu
J.
re illustrating it xplo iv lowing Tabl 1.
04 it isnote th ra tu ro rtie
71.S
90 90-92
::
87
ry ta li
is dv ntag re idin in ot ntia ha ar of th tage in th re ti ty lu tion nd itrati of rf ra or rf ra ia et te in in th ir ta th ynth si te intermixin itri ri ti rg hazard us in tabl ac ty nitrat isac mulate in
967,
nitrofurfuraJ dilCetate Melting point, Yield.
ta
ar
tr in ritain
Duration of preliminar ageing of the lCetyl nitrat solution in ICetic anhydrid at 15-20· C!em perature hour
ma ipul ti ns
ti to is lu io re gi en in th fol-
In imil mann r, th tate is reduce in th as which is id
ield S- itrofurf ra di ce nitratin rf ra di et te
ra io tu S· tion ur ur di cetate tartin itri acid (spe ific gravity I.S), concentrated sulphuri acid (specifi grav it 1.84 an acetic anhydrid were 1:2:0.036:8.8respec tively. Duration of preliminar ageing of the lCetyl
nitrat solution in aeenc anhydrid at IS-20· . h
S-
nitrofurfura
::
dilCetate Melting point.
.::-
70.2
90_91
4,052,419 Tabl Duratio
of preliminar
aaein, of th acetyl nitrat
wate -miscibl
organi
nitrofurfural diacetale
solution in IICeIic
peratllJ'e, houn
mixture, to add, into th latter solvent.
3-continue Meltin, point,
Yield,
!em.
9f,
'C
42.3
improved method of preparin
ter-miscible organi
S-nitrofurfura diacetat
solvent.
10
It is d e
·to
re pectivel
an at
r p
i.e,
·C
i.e,
as
1t temperat re rang ng ro O·t IS·
8S% of th theoretica
value)
C,
to O·to 2S· with th range
4S·
to
35
ch nica stirre an coolin -beating means. the followin
manner
furfural diace-
40
is furfu-
t s
s as to e 10 C.
y m
s of h
is advisa le that th nitratio
1:2.S-6.3 respectively.
4t
2"
2r
1.1: 4S·
to
The water-treatmen
used as of the reaction
4,052,419 C.
removal.
25% (d
2S· to
IS·
C.
sively
or
simultaneously.
C.
tion mixt re is
and
is isolated
9 0 · · -9 2 · C. 20
(O.OOIM) 2.'5
Example an
1.
isolatio
of the
vI'
30
used in
C, organi
rnl.
he
el
of 5-nitrofurfu
ia C.
is ho-
EXAMPLE
:;5
sire
product.
uf
40
.0
Example
(O.032.M)
10.2 1.
are
l:1.3:0.041:4
respectively. IS
organi so vent Fo better understandin
of
'-(
\e
fuming
SUlphuri
=.
min-
to IS· C. Thereafter.
to the
45 10
constant
tor
value 15 -25" C.
5' C) added 3.24
to S5'
(O.OOI2M) of
I.
acid (d being 90"-9 j . s o
perature 5·
IS
60
Mola ratios betwee fural, nitric acid an ---.~~-~--",-.
fur-
S-nitrofurfural discetate
~ ~~
. -
4,OS2,419 Table 4-continued Mola raciOi fural. nitric acid an
fur·
ia etat
is schemati al
hown in th ac ompanyin
'·nicrofurfural diacetll Yield.
(S
1:1..:. 1:1.':4 1:2.0:4
)p T
ad
5%
mtra!lon p~oces
(0.02sM~ of furfural .diacetate in .5
solu io
7f rw of ca st so a, th r-
Om
M)
ti
sn
nm
Ca
20
·t
nch dca
an sulphuri acid ar introduced into acetic anhydrid
2S
.ac
.Pno to th synt ~ls, th
~tra lo ch~mbe IS ill~
fUle it 10
da
On
·t
10
50 IS
added 5.
m1 and 5%
C.
to
C.
5% 3.5-4.5, IS
to 55
C.
exte na heat re oval
Mola ratiol of furfural t."
constant.
----:1-::1.-:1-:-:'------8::-:-1_;.,.6----90....=..::--91-.'.:__~
In th
xample 5-ni ro ur ural
iace at
is re ared
mllhr) Temper
4,052,419 .4 After treat en wit water artd etltralizationwith an to alka i, th reacti ixture with pH va Ueo fr ea ed th fl te er tu fr 16 is replaced with ho water) an ai tained at this te pe at re fo hour er stir in he to is at th desire pr
th theoretica
10
he
elti
poin
th pr d-
Nitratio furfural treatmen th resu ti reac ti ixture with wate an alka an is atio th esired pr duct ar perf rmed in an er si ilar to es ed fo eg Ex pl iffe ence esides in that ca bo tetrachl ri is se 10
9S ea etha iacetate is .8 (7 .4 elti poin th pr
temperatur fo hours, an the resu tin precipitatin crysta S- itrofurfural diacetat ar treate by suc6g am fu fu al intr ce into th reacti itrofurfural diacetate. Th eltin poi of the product is '- 2"
to
to
ixture .7 (0.0 SM acetic anhydrid an ichl etha havi te peratu ar si ta yd g( ff la ixture .0 (0.0 M) fu in it ic acid an .0 (O.OOO M) su phuric acid with stir in Mo ar ti fu fu hu ic acetic anhydrid ar :1.3:0.0 6: respective y. emperhe ti tained th by ea exte al heat
acetic anhy ri (0.0 SM at with te pe at re fr ·t ed .4 (0.02SM)of furfural an ixture 2. (0.0 2M fu it .0 (O.OOO fu fu
ea tu
ixtu ichl
ex er it ic an
.4 etha
ea em fu ulph ri acid ar ad ed into acetic
fter he with ichl ro etha e, th ed
et
empe
xt ti
hy id furfural
tota am
he yiel of S- itrofurfural th theo etical va e) he ct is 88
ixtu
is stirre
th ea in te at ·C
fo an ad itio fr mO
f 2 . C a d s d f r 2 in th ea tu em er fr mO·to S· si exte al heat ft ir he empe e, .1m aque us so utio causti soda to brin pH ixture is 3.S-4.S. Afterwards to th reacti
in within th ra
wi
ed
40
es hi th ea io em er hi fr ea xter ea em va ereafter ti ixture is added, de stirri .0
3.S-4.S.
emperature hereafter, ichl
ix
th
IS'
fl
ea
en er
ed em er
-2S' th reaction ixture is etha is isti ed ff in vac-
empe fo ea
wi in th
ed fr
to
excess is isti ed ff in vacu create by water-je pu (resid al pressu IS-2S
ea ),
Hg), th te peratu bein th es ti crysta in esidue is fi tere ff washed with S-2S water-bath of 20 -2S· he eactio as re ai in SO50m co wate an ried to iv .8g (7 .4 th afte th re va dich or etha by distil ing- ff is theoretica va ue of itrofurfural diacetat elti at
mac th
e-
S0 ir ea stirre fo
ed evel).
he
is
ined en to ho
at
empe fo 1h esired ed 0m er te pe at re within th an
filtered-off, washed with co wate an ie at ro te perature ina vacuum desiccat ve ph ph ru pe toxide he yiel S- itrofurfural diacetat is .7 (7 .8 th theo etical va e) he elti s9 ·Usin tetrahydrofura instead of 9S io fu fu ia et ed ie
tr
elec ed fr
em er in fr ei effe ed ep el an su ph ic acid into acetic anhydrid
6S
C; sai itrateo xt it ic havi te with co stan stir in th re ulti reacti ixture ar atio th co po bein itrate itri an ulph ri acid bein ai tained equa to :1. 2: .0 6- .041 respec tive y; said co poun an th ixtu acid bein ot s as to m ed evel
fu fu
ia et te
en
ed
he
4,052,419
11 it
lu
en at 1.1:1 to 1.8:1,
e,
he ma
et
th ec 3.S-S in th
id
ar y,
tr
ea
S· ic nd eu ti
ri ng
xt 4S
at to
th · t 2S' wi e, and
sistin of furfural an furfural diacetat with nitratin ce ni me te converting th nitrated intermediate into S-nitrofurfura ta mp me ch ri tr
tion mixture
:2.S-6.3
respectively.
12
on mi e, hl te ga nt is distille otT. he 4, wh Ii. organi chlorinate solven is se om ro consisting of dichloromethan an carbon tetrachlorid an th water-miscible organi solven is selected from ou ns ha pr l, ydrofuran an acetone. 7. In th method of preparin S-nitrofurfura diacetat
ua po
anhydride.
ul
ta
ix
us
ep to maintai
st
of he
36-0.041, respectively. ra
1:1.4
sp
ly
af
io
dd nd su
ci 10· this temperature, tu dd 1:1.1-2:0.0-
solution in acetic anhydride.
ma
in em ur ra offrom 4S to C, said reaction mixtur is mixe with tu of ac water-miscible organi solvent. 30 rinate solven at 4, th addition of th water-miscible organi solven to th
40
45
50
60
6S
yd ic hl volumetric rati of acetic anhydrid to 1:2, respectively.
• • • •
