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Патент USA US3071600

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3,h7i,5%0
United States Patent O??ce
CONDENSATION
Patented Jan. 1, 1963
1
2
3,071,590
materials in the manufacture of the compounds of this
invention are prepared by adding two equivalents of an
PRQJDUCIE
0F
FORMALDE
acid to one equivalent of a condensation product re
HYDE, PRIMARY AMINES AND KETONES
George S. Gardner, Eilsins Park, and Harry L. Faigen,
illh'.';
sulting from the reaction of a fatty or naphthenic acid
with an aliphatic diamine to form an imidazoline.
--r.5
.
Al
ll?nliiiifl’ia? :ié?i?i: iii) 335323 Pmducts’ m ’
though the preparation of the imidazoline rorms no part
No Drawing. Filed Man 19, 1959, §eL Na @0373
of the present invention, we have found that the products
formed by the reaction of a polyethylene polyamine such,
6 Claims, (Cl, 260-3095)
for example, as diethylene triamine with a saturated or
This invention relates to new condensation roducts
of formaldehyde, primary amines and ketones and, more
particularly, is concerned with the preparation of new
-
e
unsaturated fatty or naphthenic acid such as oleic, palrni
no or mixtures of these acids, are ideally suitable for
use in preparing the new compounds of this invention.
P
compositions
of matter and also with a
-
p
I
recess for Pre-
n
n
_
4
a
In general- We - havea found that
the saturated or un
o
-
paring the same.
saturated aliphatic acids, or mixtures thereof, containing
The compounds of this invention have the general for- 15 from 8 to 22 total carbon atoms are ideally suitable for
mula:
use in preparing the substituted imidazoline as described
B2C__OBZ
H
++
above. A typical example of mixed aliphatic acids is
I
sold under the trade name “Pamak l” by Hercules Pow
H'N\
N_OB’_OB’“I§T~R “Xv
G
der Company. This material is reputed to consist of
H
20 mixed saturated and unsaturated fatty acids consisting
I'M
primarily of lineolic acid (46%) and oleic acid (52.5%)
.
. 1.
I
and 1.5% saturated acids.
Other commercially avail
ggilergndB llgvjiegtliglfx?l t3;$521‘?sfgglsggilitofeggtdgx
able sources of saturated Or unsaturated acids falling with
occurrences of B must be as H' R1 is a saturated or un-
m the preferred pufvlew of the present Invention ale
saturated acid residue containing from 8 to 22 total car- 25 those Baphthe-mc aqlds such as are 801%, under the trade
bon atoms; R is derived from the reaction of formalde-
name S9191?)
nc Ailids’ gra((ifS.A 5mgmm
3 (815111011
Coma
. ese acl S a.“ enve
p? m eum an
hyde and a ketone having a replaceable hydrogen atom
pally)‘
adjacent to the carbinyl group X is an acid radica1_
areconsidered to be mixtures of naphthenic compounds
selected from the group of acids having a dissociation
wlgchhhgw molecular welghtfn [rangmg from 290-330
constant of at least 10~3 and where n and v are integers 30 Zn W?c h2g6 average mole“ “I formulas ranging from
from 1 to 2 inclusive with the provision that when n is l,
1941 34737 2‘ .
v must be 2 and vice versa in order to satisfy the valence
of the imidazoline radical.
The compounds
of this
invention
are prepared by a. 2.
.
. . .
.
step synthesis which initially involves the preparation
of a primary imidazoline salt according to Equation 1,
and ?nally the reaction of the imidazoline salt with
formaldehyde and a ketone according to Equation 11-
'
v
EQUATION I
N_CB2~OB2_NH' + HnXl
R,
BZChCB’
H‘
_3
. f
.
a
a
lentspf the and must 1.76 used for each equivalent of
substituted imidazoline in order to neutralize two ni
formaldehyde and a ketone. The desired reaction prod
!
50 ucts readily form by simply allowing a solution of the
_
_
reactants to stand at average room temperature for about
‘ where" ‘S the valence “the “1d “meal X-
EQUATION II
-
H
24 hours to about 3 days. However, if desired, the con
densation reaction may be completed in considerably
H.N
BgC-—*—~CB2
N—CBi—-CBz—-NH2' nXv+HoH0+R,-o-R, _->
(I)
1
imidazoline salt with a slight molar excess of both
?
_ R‘
\ /
f
Stant 0 at- east .10 are sans actory for use m th“ Pr-Ov
‘ 685 of the mven_non' It has been found that W’? equwa'
45 vention. We have found that the most suitable method
of preparing these new compositions of matter consists
of reacting one mol equivalent of a substituted primary
N—OB2_OB2_NH2 nXv
§C/
e se ected rom t c
dais co-nslstmg
of hydrocl-?onc’ ydro‘bl-Worm? find Sul
time acids.
In general acids having a dissociation con
Equation I, above.
The imidazoline salt obtained as the product of Equa
tion I is reacted with formaldehyde and a ketone as
shown in Equation II to yield the compounds of this in
('3
H.N
t e process 9 t is invention may
35
.
Pave been foung sultlable f? 1153;:
40 trogen atoms of the imidazoline molecule as shown in
B,C_._QB,
N\
.
hThe aclds
ll
0
R4
H.N
Bq([]-—-—.CB7
N_—oB,-oB¢-N-oH,-R2—o—1n
E'I
YLXY+HQO
\ /
(I)
-
H
H
0
R1
where B, R1, X, v and n are as described above; R2 is
shorter periods of time by gently warming the reactants
selected from the group consisting of methyl and methyl
over a steam bath.
The ketones which we have found to be Suitable for
ene radicals with the provision that in the unreacted
ketone R2 is methyl unless the ketone is cyclic in which 65 use in the process of this invention are those having a
replaceable hydrogen atom adjacent the carbonyl group,
case it is a methylene group and R3 is selected from the
class consisting of alkyl, aryl, arylalkyl and heterocyclic
and’ are selected from the class of ketones consisting of
( 1) methyl-alkyl ketones such as represented by the
groups and when taken together R2 and R3 constitute
divalent, organic residues from alicyclic rings, said resi 70 formula CH3COCnH2n+1 where n is an integer from 1
to 19 inclusive and where the alkyl radical may be
dues containing not more than 5 carbon atoms.
straight or branched chain, (2) methyl aryl and methyl
The primary amine salts suitable for use as starting
8,071,590
3
4
arylalkyl ketones such as acetophenone, methyl benzyl
ketone and methyl diphenylyl ketone, and (3) alicyclic
Example 7
H2C———~CH2
and heterocyclic ketones containing ?ve or six membered
H
‘H’
H.N\ N—CH2—CHz—I.lT—-CH:—CHl—?3'-(CH:)7-CH: 201
$151131
rings such for example, as cyclopentanone, cyclohexan
C
H
O
one and methyl thienyl ketone.
01
The condensation reaction, when prepared in ac
cordance with the above description will contain the
Z-pentadecyl, 1-(N-undecan0ne-3)-aminoethyl imidazoline dihydrochlorlde
products of the present invention in the form of their
salts. These salts are generally water soluble and sub
Example 8
stantially oil insoluble, and ?nd utility as Surface active, 10 '_H2C————CHz
H
H
emulsifying and corrosion inhibition agents Without need
H.N
N—-OHz—CHz—llT—CHz—CH:—-C—-CH;-—CH3 2B1"
of further puri?cation or modi?cation when used in
o
aqueous media.
it
(‘i
Typical examples of compounds which may be pre~
..
(EuHzl
pared by the process of this invention are listed below 15 2-undecy1,l-(N-pentanone-3)-aminoethyl imidazoline dihydrobtomide
by way of illustration but are in no way intended to
limit the scope of this invention:
Example 9
_
Example 1
Hz(|J--—-<|3H2
H
H
H2C——-——(E——CH:
111
- ++
20
H.N\ C N-CHz—-CH—ITI—-CH3—CHz-€—(OHI)10-CH:
SOF
H: H
O
H.N\ C /N—CH2—CH-z—N~CHz-CHz-O—OHz-®
304"
I]
H
0
$221545
,
_
“H20
5-rnetl1yl,2-tetradecyl,1-(N-tetradecanone-3)-aminoisopropyl
20
imidazoline sulfate
2-docosanyl,1-(N-é-phenyLbutanone-3)-amlnoethyl imidazoline sulfate
Example 10
Example 2
HgC-—-—CH:
H
H
H
CmHaa
H1O
2-undecyI,1-(N-butanone-3)-aminoethyl-imidazoline dihydrochloride
CH:
'
Example 11
35
CH:
_H:C———CH:
5-methyl,2-hexadecyLl-(N-a-methyl cyclohexanone)-amu1oisopropyl
imidazoline sulfate
Example 3
40 _.
1?:
++
O
(gizHza
2-dodecyl, l-(N-heptanone~3)-aminoethy1 imidazoline dihydrqbromide
(guHzs
Example 12
1i‘
45 FH2C—-——C—CH:
C
H2(|3—OH’
I|I
11E
++
H.N\ C N—CH2—CH2—~N—CH:—CH2—(|J—C—CH5
2C1
H
O
H:
50
_
CH: H
1-(N-4—methyl,
’
pentanone'm-aminoethyl
dihydrochloride
imidazoline
Example 13
H;C——-CH1
55
.
H
H
H
0
(5181385
H
I
H
N-CHr-CHz-liT-CHg-CHz-?-CH: 2C!“
0
H
S
imidazoline sulfate
Example 5
HzC--———C—CHs
O
?-methyl, 2-nony1, 1-(N-3-(2~thienyl),propanone-3)-aminoisopropyl
$171135
p
EC-CH
éaHn
.
2-l1e tadecyl
”
H
H.N\ /N—OHz—CH—ITT—OHz—CH:—(I%—(HJ\ /é)H SOP‘
Example 4
\
++
2-dodecyl,1-(N-docosanone-3)-aminoethyl imidazoline dihydrochloride
.
H
"
H
H.N\ C N—CHZ_CHQ‘%I"GHP‘CHT-(I~IJ‘_(CHQ)XPCH]
201H
O
H.N\ N-CHg-CHz-N-OHz-CHr?f-(CHQ3-CH3 2B1"
O
“
IELN§C N-CHz-CHrPiT-CHr-CHx-?-CH:
201'’
H
O
(‘111KB
3'0
H.N\ N-CHr-CH-N-CH-z; \
so
\o
CH; 1'1 n20
$=0 ‘
\
H
H
mo-—b-0H=
H2C-——~CH2
H
2-0ctadecenyl,l-(N-butanone-BJ-aminoethyl lrnidazoline dihydrochloride
69
Example 14
H.N§C/N—CH2—?H—N—OH:—CH:—(?—-(CH2) (-GH; 2 Cl“
OH: H
O
CIEIHZ!
E-methyl, 2-decyl, 1-(N-octanone-3)-aminoisopropyl imidazoline
dihydro chloride
Example 6
H2C-—-CH:
H
65
2-0ctyl,1-(N-tridecsnone-S)-aminoethyl imidazoline dihydrobromide
+4
SOF
2-nonadecyl, 1-(N~<liphenylyl-3, propanone-3)~aminoethyl imldazoline sulfate
3,071,590
51
6
2-pentadecyl,1-(N-butanone-3)-aminoethyl imidazoline di—
hydrochloride were as follows:
Nitrogen
Found, percent _________________ -_
Theoretical, percent ____________ __
5~methyl,2-tridecyl,1~(N-a—methylcyclopentanone)-arninoisopropyl
imidazoline dihydrochloride
8. 84
9. 02
Molecular
Chlorine Weight (On
chlorine)
15. 2
15. 2
466
466
'
Example 19
10
0.1 mol of an imidazoline prepared from the reaction
of oleic acid with diethylene triamine is added to 0.2 mol
of hydrochloric acid (20 mls. of 20° Bé..).. To the primary
amine dihydrochloride is added 0.13 mol of aqueous 37%
formaldehyde solution and 0.13 mol of acetone. The
eaction mixture is warmed over a steam bath with agita
dihydrochloride
tion for 4.5 hours. Upon completion of the reaction the
entire product is diluted with water to yield a ?nal solu
Speci?c examples of the preparation of compounds fall
tion containing approximately 49 grams of crude inhibitor
ing under the purview of this invention are listed below 20 in 15-0 mls. of solution.
by way of illustration but are in no way intended to limit
A sample of the crude product resulting from this re
the scope of this invention.
action was puri?ed as described under Example 17 above.
Example 17
Resulting analyses from the puri?ed 2-heptadecenyl,1-(N
0.1 mol of the substituted imidazoline prepared by the
reaction of diethylene triamine with lauric acid is mixed
with 25 mls. of isopropyl alcohol which is ‘added for sol
butanone-3 ) -aminoethyl imidazoline dihydrochloride were
vency purposes. This solution is then added to 0.2 mol
(20 mls. of 20° Bé.) of hydrochloric acid to form the
primary imidazoline dihydrochloride salt. To this salt
solution is added ‘0.13 mol of aqueous 37% formaldehyde
solution and 0.13 mol of acetone. The reaction mixture
as follows:
Nitrogen
Molecular
Chlorine Weight (On
chlorine)
Found, percent _________________ __
8. 68
14.4
492
Theoretical, percent ____________ __
8. 56
14. 4
492
I is allowed to stand at ambient temperature (about 25° C.)
for 1 day. After about 24 hours the reaction cycle was
considered to be completed and the entire reaction mix
Example 20
0.1 mol of an imidazoline prepared from the reaction
of oleic acid with dipropylene triamine is admixed with
25 mls. of isopropyl alcohol. This solution is then added
to 0.2 mol of hydrochloric acid (20 mls. of 20° 136.).
A portion )of the crude product resulting from Example
17 was puri?ed by evaporating a sample of the aqueous 40 0.13 mol of aqueous 37% formaldehyde solution and 0.13
ture was diluted with water to yield a ?nal inhibitor solu
tion containing approximately 41 grams of product in 150
mls. of solution.
solution to dryness over a steam bath. The dried residue
was then dissolved in acetone and ?ltered hot to remove
unreacted primary imid‘azoline salt. Upon cooling a
product separated from the ?ltrate. This precipitate was
recovered and reprecipitated from acetone. Analysis of
the puri?ed Z-undecyl,l-(N-butanone-3)-aminoethyl imid
azoline dihydrochloride after ?ltration and vacuum dry
ing was ‘as follows:
Nitrogen
Molecular
Chlorine Weight (On
mol of ‘acetone are then added to the primary amine di
hydrochloride. The solution was gently heated with agi
tation to reflux and held in this condition for 3.5 hours.
Upon completion of the reaction cycle the. product was
dissolved in water to yield a ?nal solution containing
approximately 52 grams of crude inhibitor in 157 mls. of
solution.
A sample of the crude product resulting from this re
action Was subjected to the puri?cation technique as de
scribed under Example 17. The puri?ed inhibitor ana
lyzed as follows:
chlorine)
Found, percent _________________ ._
Theoretical, percent ____________ -_
10.1
10. 25
17.3
17. 3
0.1 mol of the substituted imidazoline prepared by the
reaction of diethylene triamine with palmitic acid is mixed 60
This solution is then
added to 0.2 mol of hydrochloric acid (20 mls. of 20° 36.)
to form the primary amine dihydrochloride salt. 0.13
mol of aqueous 37% formaldehyde solution and 0.13 mol
Molecular
Chlorine Weight (On
chlorine)
Found, percent _________________ -_
Theoretical, percent ____________ __
Example 18
in 25 rnls. of isopropyl alcohol.
Nitrogen
410
8. 60
8.08
14. 2
13. 7
500
520
Example 21
A sample of Sunaptic Acids A, de-oiled by the Sun Oil
Co. by solvent extraction, was vacuum distilled with the
fraction boiling between 173 °and 210° C. at 1 mm. Hg
being recovered. 132 g. of the distillate was admixed
of acetone are added to the salt and the reaction mixture 65 with 75 ml. of diethylenetriamine and 50 mls. benzene.
is allowed to stand at ambient temperature (about 25 ° C.)
This mixture was heated gently to re?ux (150° C. max.)
with continuous stirring for 3 days. After completion
and held at this temperature for 24 hours with continuous
of the reaction cycle the product remained in solution and
water removal. The resulting product was vacuum dis
was diluted with water to yield a ?nal inhibitor solution
tilled (1 mm. Hg) to recover the Z-imidazoline of mixed
containing approximately 47 grams of crude Z-pentadecyl, 70 naphthenic acids.
l-(N-butanone-3)~aminoethyl imidazoline dihydrochlo
42 grams of the distillate was dissolved in 25 ml. of iso
ride in 150 mls. of solution.
propyl alcohol and was then added to 20 ml. of 20° Be.
A portion of the crude product resulting from Example
18 was puri?ed according to the procedure outlined under
hydrochloric acid to form the primary amine dihydro
chloride salt. To this salt was added
mls.,of aqueous
Example '17 above. Analyses resulting from the puri?ed 75 37% formaldehyde solution and 10 ml. of acetone. This
3,071,590
Example 24
mixture was heated gently to re?ux ‘and held in this con
dition for a total of 15 hours with continuous agitation.
Upon completion of the reaction cycle, the product was
0.1 mol of the substituted imidazoline prepared from
the reaction of palmitic acid and diethylene triamine was
diluted with su?icient water to yield a ?nal inhibitor solu
dissolved in 25 mls. of isopropyl alcohol. This solution
tion containing approximately 45 grams of product in
was then added to 0.2 mol (20 ccs.) of 20° Bé. hydro
150 mls. of solution.
chloric acid at a slow rate with cooling to form the pri
Partial puri?cation of a sample of the product resulting
mary amine dihydrochloride salt. To this admixture was
from Example 21 was accomplished according to the pro
added 0.13 mol of aqueous 37% formaldehyde solution
cedure as described under Example 17. The partially
and 0.13 mol of cyclohexanone. The reaction mixture
puri?ed product was dried in vacuum at the boiling point 10 was heated to 100° C. and held at this temperature with
of C C14. Analyses were as follows:
continuous stirring for twenty minutes. After the reac
tion cycle the crude product was dissolved in additional
Nitrogen
Chlorine
water to yield a solution containing approximately 51
grams of inhibitor in 15 0 mls. of solution.
Found, percent ______________________________ __
9. 45
17. 4
A sample of the crude 2-pentadecyl,l-(N-u-methyl
cyclohexanone)-aminoethyl imidazoline dihydrochloride
Example 22
0.1 mol of the substituted imidazoline prepared by the
reaction of diethylene triamine and lauric acid was ad 20
mixed with 25 mls. of isopropyl alcohol. This solution
was then added to 0.2 mol (20 ccs.) of 20° Bé. hydro
chloric acid with cooling to form the primary amine di
hydrochloride salt. To this admixture was added 0.13
mol of aqueous 37% formaldehyde solution and 0.13 mol 25
of acetophenone. The reaction mixture was gently heated
to 100° C. and held at this temperature range for 1.5 hours
with agitation.
Upon completion of the reaction the
product was diluted with su?icient water to yield a ?nal
inhibitor solution containing approximately 47 grams of
crude 2-undecyl, 1-(N-phenyl-3,-propanone-3)-aminoethyl
was puri?ed according to the method noted above.
sulting analyses were as follows:
Nitrogen
Re
Molecular
Chlorine Weight (on
Chlorine)
Found, percent ______ ._
7. 93
13.08
544
Theoretical, percent..-
8.32
14. 03
506
Example 25
36 grams of substituted imidazoline prepared by the
reaction of diethylene triamine with a commercial grade
of mixed fatty acids sold under the tradename “Pamak 1”
were admixed with 25 mls. of isopropyl alcohol. This
solution was then added to 20 cos. of 20° Bé. hydrochloric
imidazoline dihydrochloride in 150 mls. of solution.
A portion of the crude Z-undecyl,1-(N-phenyl-3,pro
acid with cooling to form the primary amine dihydro-
panone-3)-aminoethyl imidazoline dihydrochloride pre
chloride salt.
To this admixture was then added 10 ccs.
pared in Example 22 was puri?ed as described above, with 35 of aqueous 37% formaldehyde solution and 10 ccs. of
the recovered product analyzing as follows:
acetone. The reaction mixture was allowed to stand at a
temperature ranging from 25—30° C. for sixteen hours.
Molecular Weight
Upon completion of the reaction the product was diluted
Nitrogen Chlorine
with su?icient Water to yield a ?nal inhibitor solution con
On Chlo- On Nitro 40
rine
gen
Found, percent ____________ __
Theoretical, percent _______ __
8.91
8.90
14.4
15.0
493
472
472
472
taining approximately 51 grams of product in 150 mls. of
solution.
Inhibitor solutions prepared as described in Examples
17 to 25, inclusive were tested for corrosion inhibiting
values according to the procedure of Gardner, Faigen,
Gibson and Hall, Journal of the Franklin Institute, Volume
xample 23
262, No. 5‘, pages 369—384 (1956). This test consists of
immersing a 1/2" x 7" x 0.030" SAE 1010 type metal strip
0.1 mol of the substituted imidazoline prepared from
into a solution containing 30 cc. washed mineral spirits,
the reaction of diethylene triamine and palmitic acid was
30 cc. of 4% aqueous sodium chloride solution and 1000
dissolved in 25 mls. of isopropyl alcohol. This solution
was then added with cooling to 0.2 mol (20 ccs.) of 20° 50 parts per million of hydrogen sul?de (calculated on the
brine volume). The testing temperature is 40° C. and is
Bé. hydrochloric acid to form the corresponding primary
continued for 24 hours. Inhibitor solution was added to
amine dihydrochloride salt. 0.13 mol of aqueous 37%
the corrosive brine in amounts to yield a ?nal concentra
formaldehyde solution and 0.13 mol of methyl ethyl ke
tion of 50 parts per million of the brine. Results of these
tone were added to the reaction mixture, and the solution
tests are reported in Table I and corrosion values are ex
was allowed to remain at ambient temperature (about
25° C.) for 16 hours with continuous agitation. After
the 16 hour reaction cycle had been completed, the crude
pressed in terms of mg. of weight loss of the test strip.
product was dissolved in sul?cient water to yield a ?nal
Inhibitor solution from Example No.:
inhibitor solution containing approximately 48 grams of
crude 2-pentadecyl,1-(N-pentanone-3) - aminoethyl imid
TABLE I
60
Control
7.3
18
5.4
20
lyzed as follows:
23
Nitrogen Chlorine
On Chlo- On Nitro
rine
gen
Found, percent ............ -_
8. 62
15. 7
453
488
Theoretical, percent- - _ .. _..--
8. 76
14. 8
480
480
70
48.0
17 ___________________________________ --
azoline dihydrochloride in 150 mls. of solution.
A portion of the crude inhibitor resulting from Example
23 was subjected to the puri?cation procedure described
under Example 17. The puri?ed 2-pentadecyl,1-(N-pen
tanone-3)-aminoethyl imidazoline dihydrochloride ana 65
Molecular Vl’eight
ct’ié?ill’iaé’ég'
_.____
____ __
_.__
19 ___
21
22 _____ __
_....._
..___
____ __
_.
_
4.6
4.9
6.3
4.8
3.8
24 _____-
3.3
25 ___________________________________ ....
4.4
As noted above the compounds of this invention are
water soluble and substantially oil insoluble, and ?nd use
as exceptionally effective corrosion inhibition agents when
employed in aqueous media. However, if it is desirable
to obtain corrosion inhibitors which are oil soluble and
75 substantially water insoluble, it is only necessary to con
3,071,590
‘2. 2-heptadecenyl-1-(N-butanone~3) - aminoethyl imid
vert the imidazoline salts of this invention to their corre
azoline dihydrochloride having the formula:
sponding free bases.
Various methods may be employed to accomplish this
conversion. For example, the inorganic salts resulting
from these reactions may be treated by careful neutraliza
tion in the cold with a dilute base such as sodium or am
monium hydroxide or sodium carbonate solutions. How
ever, the preferred method of converting these salts to their
3. S-methyl-Z-hexadecyl-l - (N - alpha - methyl ~ cyclo
free bases consists of passing an isopropyl alcohol solu
hexanone)-aminoisopropyl
imidazoline sulfate having the
tion of the salt through a column containing a strong base 10
formula:
quaternary ammonium type ‘anion exchange resin. We
have found that Amberlite IRA 401, which is a resin of
this type as sold by the Rohm and Haas Company, if pre
treated with dilute caustic solution, will readily convert
these salts to their free bases. Recovery of the base is
readily accomplished by evaporating the solution and
drying the product in vacuum.
In order to demonstrate this conversion technique, a
sample of 2-undecyl,1-(N-butanone-3)-aminoethyl imid
azoline dihydrochloride as per Example 10 was dissolved 20
4. Z-heptadecyl-l-(N-4-methyl, pentanone-3) - amino
in 100 mls. of 90% isopropyl alcohol. A 100 ml. capa
ethyl imidazoline dihydrochloride having the formula:
city column containing 60 grams of Amberlite IRA-401
was washed successively with 8-bed volumes of 4% so
Hq(|3-———CH2
}|I
Flt
H’
dium hydroxide solution, S-bed volumes of distilled water,
and l-bed volume of isopropyl alcohol. The alcoholic
H-N
N-CH,~cH,—N—0H,—oH,—%-c—0H3 201
solution containing the dihydrochloride salt of the in
hibitor was then passed through the column, recovered,
solvent evaporated and dried under vacuum. Analysis
of the recovered product was as follows:
5. 2-undecyl-1-(N-butanone - 3) - aminoethyl imidazo
30 line dihydrochloricle having the formula:
Nitrogen
Chlorine
Found, percent ____ __
12.1
nil
Theoretical, percent__
12. 48
none
35
We claim:
1. A compound of the formula:
6. Z-undecyH-(N - phenyl - 3, propanone - 3) - amino
ethyl imidazoline dihydrochloride having the formula:
HMIJ
CH2
H.N
N~CHz—CHr-N——CHg—CHz-(|]3—R" RX‘’
0
1&1
1'1
**
0
wherein R’ is selected from the class consisting of alkyl
and alkenyl of 8 to 22 total carbon atoms, R" is selected 45
from the group consisting of alkyl of from 1 to 19 carbon
atoms, phenyl, benzyl, biphenyl and thienyl; X is an acid
radical selected from the group consisting of Cl, 80,, and
H3O
(EH1
H-N
N—CHu~CHz-—N——CHa—CHr-([3—® 201
(|)/
I:l'[
fr
‘H’
6
(1111122
References Cited in the ?le of this patent
UNITED STATES PATENTS
Br; n is an integer from 1 to 2 inclusive, and v is an integer
inverse to that of n whereby to satisfy the valence of the
2,485,309
2,514,508
2,794,808
imidazoline radical.
2,875,210
Nunn ________________ __ Oct. 18,
Nunn ________________ __ July 11,
Albrecht et a1. _________ __ June 4,
Bollenback et al _______ __ Feb. 24,
1949
1950
1957
1959
—
UNITED STATES PAT
:
ENT OFFICE
CERTIFICATE OF CORRECTION
January
Patent N00
17 1963
3.071590George
S, Gardner et al,,
n the above numbered pat
].d read as
pears i
ertified that error ap (1 Letters Patent shou
It is hereby c ction and that the sai
ent requiring corre
corrected below.
for "HnXl" Pea? 1')—— HnX(1)
"1" read ~
41:3l
Column 1‘! line
footnote
--;
line 52, for the
Signed and sealed this 6th day of August 1963”
(SEAL)
Attest:
ERNEST W. SWIDER
Attest'ing Officer
DAVID L. LADD
_
Commissioner of Patents
‘\
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent Non 3,071,590
January 1, 1963
George S. Gardner et alt,
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 1“ line {I3i for "HnXl" rea
line 52, for the footnote "1" read ——
—— HnX(l)
l) -—D
Signed and sealed this 6th day of August 1963,
(SEAL)
Attest:
ERNEST w. SWIDER
Attesting Officer
DAVID L‘ LADD
Commissioner of Patents
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