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Патент USA US2406186

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2,406,186 1'
Patented Aug. 20, 1946
~ UNITED ‘sures PATENT/omega ‘~
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I. I [2,406,186
‘ : ,MANUFACTURE OF SURFACE-ACTIVE
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COMPOUNDS,
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'_ ‘Alfred
William‘ Baldwin, Noel William-Cusaand
Henry 'Worthington,
Blackley, a, ‘Manchester,
, I
v 1; England, assignors to Imperial Chemical Indus- , _.
‘ v tries-Limited, a corporationpf Greatpritain
‘
‘ ' No Drawing. 'Applicationilanuaryiid,194§Q8crial
’
In Great BritainJanuarym30,
No. 472,388.
1942, .
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invention ‘relates to the‘ manufacture ‘of
new ‘surface-active compounds.
‘ I‘ controllable rate. Theuoptimum temperature (16- '
More particu-‘
pends .on the. particular oxazolidinefand amine
used.’ "In practicenit is convenient ,to heat thev
larly itlrelates to themanufacture of new ,sur- '
Iace-active'icondensation products of primary or
secondary amines with particular,2,5-diketoox
amine, ,(tovgetherrwith the ‘solvent,’ if one is used) _
and toadd the oxazolidine gradually making each
subsequent addition ‘when the evolution of carbon
azolidines of the kind“hereinafter speci?ed,
dioxidejhas slackened off,
‘We have now found that new surface-active
compounds, useful as wetting agents, detergents,
softeningx agents, emulsifying or dispersing agents
are:obtained by causing; a primary or secondary
1 it is?belie'ved that the Jensen, 0: equinoieeii-j
lar proportions of amine ‘and ,oxa‘zolidine canjbe
represented,'using ‘a’ primary aminei' ANHz for?
amine to interact with one-lot; more molecular
proportions ‘of a 2,5sdiketooxazolidine of. the for?‘
mulay
‘
'
nN-oo-o
‘i
‘R’.
11%00
'
illustration,
A.NH: + RN-—C
by'the
0-0 equation
A.NH.CO';CHR’.NH.R
'
‘ +" e05
‘
:
,
“BLOB-9500i
.
.
When'i'inore‘than one 'rnolecularproportion oi
'
‘ ' oxazolidine is used
wherein R and B’ may each be a hydrogen atom ,
the reaction- is believed to jbe
or, onerof them;,-but not both, may- be a methyl
group,
I
r
,
1
V
-
A.NH;‘+nRi_\r-co-1o"f=>
' R':0H——V—('JO
A.Nn.ooonnwmo'oonngrrm,.-1.HY+’nool
"
' 7
"
‘T
,
The 2,5 diketooxazolidines;which are used as 20
starting‘ materials may themselves be :made by
oausing‘an e-aminofoarboxylic acid-,o? the ,for-; V
mula RNH-—R'.C1I-I¥COOH to ‘react-with .a chlo
roformic ester CICOQX, whereby the compound
XOCO—NR—R'CH—COOI~I is formed, or by 65
terifyingth'ersaid acid andv then-treating it With
carbon dioxide in; the cold -(in._the,,ma1nn,er de7
Example 1
25
‘scribed, in Nature,..l939, VQLIAAJVD; 83-2) whereby ,
' the i-compound XOCO.——B'CH—NBQCOOH ‘is
formed, the said compound
'
-
'
xocoeuaeafouaooou"
while ‘11.5 parts of 3-methyl~2,5-diketooxazolidine
are gradually added in portions, each- successive
evolution of carbon dioxide’ being ‘allowedtocease
beiqre the nextaddition is made, The benzene
ic'pressure at 100° C. There remains a pale‘yel
low waxy solid which is only slightly soluble in
hot water but completely soluble in dilute aque
acidinto the corresponding carboxylic halide,v for
example, a phosphorus halide or ox-yhalide, phos
gene or thionyl chloride, followed by heating to
effect ring closure and elimination of the halide
X-Hal. In these formulae ;;stands for an alkyl,
’
26,9 partsof octadecylamine are dissolved ‘at
rid-{50°C. in‘, 200 parts‘ of dry ‘benzene and. the
solution isstirred and‘ kept at that‘ temperature
is ‘then removed by distillation, ?rst at atmos
pheric pressure and ?nally under sub-atmospher
'
or XOCO—R'CH—'NR-'-C'OOH- being? then treat
ed with an agent adapted to convert a‘carboxylic
‘cycloalkyl or aralkylradical,
‘The ‘following examples illustrate, but do not
vlimi_t,_,the invention. o The parts are by weight.’
ous hydrochloric acid, forming a clear foaming
solution.
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‘
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' - ‘ Example 2'
,40
n
'
' The u-amino acids from which may be‘ derived
the 2,5 diketooxazolidines which are to be used as
starting“ materials for this invention are there
To 26.9 parts of octadecylamine dissolved in
5.00 parts ‘of dry benzene at 45-50‘ C. there: are
added 57.5 parts of 3émethyl-2,5§-diketooxazoli
fore glycinez sarcosine and alanine.‘ Oxazolidines
‘lerived, iron;
.
mixtures~ of these a-amino acids -
dine,_ the, addition being made gradually in the
may be mentioned, for,examplqoctadecylamine,
:powder', whichv dissolves in hotlwater forming: a
way described in Example 1,. {- The benzeneis'then
distilled o?, ?rst at atmospheric pressure‘van‘d
maralsoibe 135?‘.1,
>
then under sub-atmospheric pressure,- whereupon
‘ As suitable, primary or‘ secondary amines to
be combinedwith the 2_,'5_;diketooi;az,olidines there . - there remains a’ pale yellow, slightly hygroscopic;
50 ‘clear'foaming solutfignt
amine’, ?TnapIithyIamineandI piperidine, ,1
._
‘ i
,‘
' The ‘reaction "of thefoxazolidinewith the amine
is broughjJ about‘ by; heatingv them together,‘ op;
tionally in preseneeof'an‘ organic solvent, at such
a temperaturehthat carbonid _ _ gide'plis evolved at a 55.
i
I
H
‘ ‘Example 3
‘
“134.5 ' seas , of 3_-methyl-2',‘5,r-diketooxazolidine
‘are-‘added to a solution oi5'.38 parts of octadecyl
~{airline i_n_400 parts, of dry benzene‘ at fl5--50f",Q.1in
»
r
,-
3
4
r
easily dissolves in cold water, forming a clear so- ‘
the way described in Example 1. The benzene
. is then distilled o?, ?rst at atmospheric pressure
lution.
and then under‘ sub-atmospheric pressure? where
g
by there- isobtainedr‘a'j'creamgcoloured powder; '
I
.
V
p
Examplelll
H
__
r
._ 7 was pi \octadecylamine are dissolved in 250
which dissolves in" cold’wateryfOrmiri‘g a clear 5 parts of dry chloroform at 58-60°,C.
foaming solution.
'
_
'
I
Example
4
l_
‘
15 parts
iofi4-methyl-2,5-diketooxazolidine are added in
.
‘portions, as described in Example 1. The chlo
I
'ro'forml is then' distilled 01f under sub-atmos
5.38 parts of octadecylamine'are-‘dissolved{inks' pheric
.1600 parts of dry chloroform at 45—5Q° C.‘ ,To this
pressure.
There is thus obtained a cream
coloured waxysolid. :which is soluble in hot wa
solution there are added 69___part_sjof, 3-inethyl-.;.
2,5-diketooxazolidine in the" mannerguescribeam 7'
iter‘ to givea clear-foaming solution.
Example'l." The chloroform‘ishistilledIoi‘l', ?rst-‘j;
..
ff'ffjlvivample 11
7
7 '
.
I15, parts of t4-methyl-2,5-diketooxazolidine rare
at atmospheric pressure and then under sub‘- '
. atmospheric pressure whereby-.;-there‘lisiobtained '
Yadded' in'portionsr?in the manner described in
a light brown brittle powderiwh'ichi'is easily‘solu
7 Examplejl and’atia temperature of 40° C., to a
~ ‘ ble in cold water forming a clear foaming solu
7 solution of 3.5 parts of octadecylamine dissolved
tion.
in;;90 parts of chloroform. When the evolution
_
.
y
’
Example
7
5
.
of carbon dioxide is complete, the chloroform‘is
20
distilled o? under sub-atmospheric.pressure._.1 .The
residue is then Washed with/ether;wherebyithereh
f" Te; fa solutidniof 7.3liiartré . of . ii¥5lityi5i?iné?h
750, parts ' _.ofv .dry chloroform at. 45550", f 0.,‘ v5.7.5
' is obtained, ajcream coloured waxy ‘ solidwhich
is soluble. in cold‘ .water "to "give. a ‘ clear-{foaming
partslof- S-methyL-Zjidiketooxaaolidine ‘are grad; ‘
ually added in themanner}.vdescribed in§Example >
solution:
1,, The chloroform iisv then distilled; off,‘ ‘?rst at
.
y' _.
atmospheric pressure/and then§_,-_under sub-at;
,7
A.
.
"f'Era'mpZe. 12
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h
4.6 parts: of octadecylamine are dissolved'f'in
60Vparts. of dry benzene,‘ and 17.5 parts 'of 2,5411; *
k'etooxazolidine are added. “ The‘ mixture ?'is re:
mospheric pressure, vwhereby{there is obtained a
_-ligihtlbfown, hygro'sopia-sticky'gsolidlwhich dis- 7
1 solves .easilyin' cold Water, ,ror'mingga'clear "
_. lution which foams slightlyfon?shaking:
,
?ux'ed-for 12'hour's.“ The ‘benzene ‘is. thenxdis
tilled off under subhatmospheric. pressure; where-=
:by-‘a,v cream . coloured ? brittle".v .solid ' is "obtained; 7
This is partiallyfsoluble in hot water to giveia
_ V T ‘a 1.1mm of:Nemethylcetylamineiare"dissolved .
' at.45:59".iQqin??q-parts oi;.;dry chlorofprmzand '35.
the isolation-is stirred and keptv at that temper:
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sample-1s
SIITov 4.6 parts" orN-cetylmetliylamine dissolved
ature while 23 partsof 3émethyl-2L5ediketooxa_ .
zolidine are gradually added in the way'fdescribed
in Example 1.
hazy foaming solution...v
inVS'O parts fof'fdry acetone‘ at 45'*—50° C;, 18.5 ‘parts
'4 distilled v
The chloroform‘ is then
of 2.5-diketooxazolidinelare gradually addedifin '
o?i?rstiat. .atmospheric pressure and then‘ under
the ' manner described»,in iExample‘tl." 5'The1ace
sub-atmospheric.vpressure. whereby there is 50b '40 tone‘ is'then distilled‘ off‘under sub-atmospheric
tained an. orange‘. brittle powder. which dissolves
pressure whereby there is obtained'a palev brown‘
in cold water, ‘forming a clear foaming solution.
solidwhich dissolves in hot» or cold waterfform-v ‘
ing' slightly hazy solutions which 'foam when
Example. 7.
I "Toi a‘jsolution of ‘35 parts‘ of 'cyclol'féxylamine
Shaken;
. inifl?llparts of dry. chloroform at 45-509 C. there
aree'raauany: addedLin“ me'way described in Ex
atmospheric? pressure; and j-then". {under sub-at; to
pale brownish-yellow',"lhygroscopic powdenvvhich .
easily~ dissolves in’ cold~water forming’ a‘ clear
J
"j
:IExampZeB;
.
*
Y‘
‘Ill
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..
understood that the invention is notvlimited to
the particular embodiments théreindescribed, but
only
,Weclaim:
as
Process
de?ned-in
for
-. Y- the
thefollowing'claims.
_ manufacture
1
w ; ~ of
7. t_;surface-_
t
V
V
V
56 activecompounds which comprises/gradually, add
57.5 parts" or 3-methyl4'2,5-dikétooxazolidine
ing- a~2,5-diketooxazolidine of the formula,
are added to a solution of 7.15 parts of pénaph
thylamine in 750 parts of ‘dry chloroform at 45
5Q°,C.,_the addition. beingv made gradually?in the
way‘described in Example ‘If. “The chloroiorm is
their 'disvtilled'o?f, ?rst ‘at. atmospheric pressure
by?there is obtained acream-coloured ‘brittle
powdervwhich dissolves in hot water, forming. a
clear solution. 7
-;
wherein
“ ‘1"’
one ofR.n-N-bo-o
R’—
andH_-_'—'-_o
Rf is .hydrog‘e'njand
y : w‘ ' 7_ _ the
60
other is selected from the class consisting of hy
drogen and methyl to a solution,,in. aninert I
‘and théniund'er ‘sub-atmospheric pressure where'
organic solvent, of a monoamine having hydro{
gen on the amino nitrogen and having the re
65
maining valencesof the nitrogen satis?ed by by?
,clrocarbon, -,the solution being heated to a tem
l-"roiiii‘pms of piper'minedisoivea ii; 400 5mg
peraturesu?icientftoycauseievolution of carbon v
of“ dry chloroform at 45-5VQ°;Q.:>there1 areadded"
the :_-diketooXazolid-iiie being I added {as 1 evolution,’ '
V 115 parts of 3-methyl-2,5-diketooxazolidine,‘ the 70
addition being made Hither-Way described in Ex
ample 1.“v The'chloroform is then, distilled .off
?rstjiat‘"atmosphericflpressure and‘ then under.
V
"
- the above examples, and! accordingly it is-tolbe
mospheric pressure-a .‘The‘re is thus obtained .a
I I
-
of thisinvention' other than"v those ‘set forth
diIlBJ QThe bhl'ol‘ofo'rm is then. .distilledfoff’?rst at
I‘ _
'
spirit and scope thereof, to devise embodiments
ample11;.57.5 parts of. 3¥methyl52,5;diketooxazoli
slightly foaming-solution.
-
JIt will be ‘apparent, to one ‘skilled in the art
that ;it'= is‘ possible.‘ without departing from ;' the
dioxide. on: addition of the :diketooxa'zolidine- and
of’ carbon‘ dioxide slaqkerisiand 411115111. at-leasiene
'mol. .per. .. o1 offamina has been added. -,as<1.re'
movingthesolvent by distillation. .. r.
12- 300.953 $0.! thev manufactureibfjfsilifaqél
subiatmospheric pressure; . Therefiis; thuslob
active compounds whichucomprises gradually add:
tained. a yellow . hygroscopicv brittle l resin which
ing '3-methyl-2.5-diketooxazolidine to a solution,
2,406,186
5
in an inert organic solvent, of a primary alkyl
amine, the solution being heated to a tempera
ture su?icient to cause evolution of carbon di
oxide on addition of the diketooxazolidine‘and
the diketooxazolidine being added as evolution of
and until at least one mol, per mol of amine, has
been added, and removing the solvent by distil
lation.
5. Compounds of the formula
carbon dioxide slackens and until at least one
mol, per mol of amine, has been added, and re
moving the solvent by distillation.
wherein n is an integer from 1 to 30, R2 is hy
-
drocarbon, A is selected from the class consisting
of hydrogen and hydrocarbon, one of R and R’
is hydrogen and the other is selected from the
class consisting of hydrogen and methyl.
6. Compounds of the formula
3. The process for the manufacture of surface
active compounds which comprises gradually
adding a 2,5-diketooxazo1idine of the formula
wherein one of R and R’ is hydrogen and the 15 wherein n is an integer from 1 to 30, R2 is hy
other is selected from the class consisting of hy
drocarbon, A is selected from the'class consisting
of hydrogen and hydrocarbon.
.
drogen and methyl to a solution, in an inert or
'7. Compounds of the formula
ganic solvent, of cetylamine, the solution being
heated to a“ temperature su?icient to cause evo
lution of carbon dioxide on addition of the 20
diketooxazolidine and the diketooxazolidine be
wherein n is an integer from 1 to 30 and R2 is
, alkyl.
ing added as evolution of carbon dioxide slackens
and until at least one mol, per mol of amine, has
8. Compounds of the formula
R2I-IN(-—CO—CH2—N_('CH3)-)1IH
been added, and removing the solvent by dis
25
tillation.
4. Process for the manufacture of surface
C1sH3'1—NH(—-CO——CH2—N(CH3) —) nH
wherein n is an integer from 1 to 30. V
active compounds which comprises gradually
9. A compound having a chain containing
from one to 30 units of the formula
adding a 2,5-diketooxazolidine of the formula
30
wherein one of R and R’ is hydrogen and the
wherein one of R and R’ is hydrogen and the
other is selected from the class consisting of hy
drogen and methyl, the terminal valence of the
other is selected from the class conisting of hy
drogen and methyl to a solution, in an inert or
ganic solvent, of octadecylamine, the solution
monovalent radical and the terminal valence of
the chain stemming from NR is satis?ed by hy
being heated to a temperature su?icient to cause
evolution of carbon dioxide on addition of the
diketooxazolidine and the diketooxazolidine be
ing added as evolution of carbon dioxide slackens 40
u
chain stemming from the CO is satis?ed by a
drogen.
'
ALFRED WILLIAM BALDWIN.
NOEL WILLIAM CUSA.
HENRY WORTHINGTON.
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