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Патент USA US3083153

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3,083,143
United States Patent O
Patented Mar. 26, 1963
2
1
drogen, alkyl, alkoxy, alkylol, alkenyl, acyl, aralkyl or
3,083,143
cycloalkyl, and 2: an integer from 1 to 3.
FLUORIDES OF ORGANIC BASES AS WELL AS OF
AMPHOTERIC COMPOUNDS, A METHOD FOR
THEIR PREPARATION, INCLUDING THE APPLI
CATION OF SUCH NEW COMPOUNDS IN THE
(d)
N-orn
CARIES PROPHYLAXIS, NEW DENTIFRICES
1'11
AND MOUTH WASHES AS WELL AS A METHOD
FOR THEIR PREPARATION
Hans Schmid, Muttenz, and Hans Rudolf Miihlemann,
wherein R’ is hydrogen, alkyl, acyl, alkenyl, alkylol,
aralkyl or cycloalkyl,
Zurich, Switzerland, assignors to GABA A.G., Basel,
Switzerland, a Swiss company
(e)
No Drawing. Filed July 11, 1958, Ser. No. 748,570
Claims priority, application Switzerland July 13, 1957
15 Claims. (Cl. 167—93)
——CO-—NII—CH-.-—(|JHOH
RI
wherein R’ is hydrogen or a lower alkyl, and
(I)
R’
The invention relates to surface-active hydro?uorides
of organic bases as well as to hydrofluorides of ampho
teric or weakly basic non-ionogenic surface-active com
pounds. The invention also relates to a method of pro
ducing such hydro?uorides and to their application as
caries prophylactics. Finally the invention relates to 20
wherein each R’ is hydrogen or a lower alkyl.
novel preparations for the care of mouth and teeth, such
The hydrolluoridcs according to the invention are solu
as dentifrices and the like.
ble in water and generally also in methanol and ethanol.
Research in recent years has revealed that the element
The aqueous solutions foam and have a weak acid re
?uorine plays an important part in the composition of
ens-drier:
dentine and that a de?ciency of this element leads to an 25 action.
In mixture with anion-active compounds such as
alkyl sulphates or alkyl-aryl sulphates mutual precipita
increased tendency of the teeth to dissolve in acids thus
reducing their resistance to caries. It is also known that
the acids which are responsible for the slow dissolution
of the dentine of the tooth are formed by bacterial ac
tion with the simultaneous reduction of their foam-form
ing ability may result.
Useful hydro?uorides having the above mentioned
tivity or by the enzymatic decomposition of particles of 30 general formula
R.X.HF
food.
By providing a sufficiency of the element ?uorine the
acid solubility of the dental enamel can be signi?cantly
are for instance compounds of the following composi
tion, but the invention is not to be considered as being
limited to the classes herein enumerated:
reduced, the introduction of the ?uorine being possible
prior to dentition through the medium of the blood and 35
after dentition by external application. For the latter
purpose ?uorine has generally been used in the form of
wherein R is alkyl, alkoxy, alkenyl or alkylol containing
an inorganic compound, for instance in the form of an
alkali metal, such as a ?uoride of tin, as a silico?uoride
or as a complex ?uoride of elements of the 4th group of
8 to 20 and preferably 12 to 18 carbon atoms or substi
tuted or unsubstituted aralkyl with 8 to 20 carbon atoms
and preferably 10 to 18 carbon atoms and both x and y
are integers from 1 to 3;
the periodic system (Brit. Pat. No. 644,339).
It has now been found that surface-active substances
(2)
of weak to strong cationic activity containing ?uorine in
R’
R—CO—NlI—CH;—-Cll'1—N/ .IIF
an ionisable bond are outstandingly suitable by external
application for reducing the acid solubility of the teeth. 45
RI
Especially suitable compounds of this type are of the
wherein
R
is
alkyl
or
alkenyl
containing
7 to 19 carbon
general formula
atoms, and each R’ is hydrogen or alkyl, alkylol, alkenyl,
aralkyl or cycloalkyl;
wherein R stands for alkyl, alkoxy, alkenyl or alkylol 50
RI!
with 8 to 20 atoms of carbon and preferably 12-18
atoms of carbon or substituted or unsubstituted aralkyl
with 8 to 20 carbon atoms and preferably 10 to 18 car
bon atoms, and X is one of the following groups:
(R)
wherein R is alkyl or alkenyl with 7 to 19. preferably l1
55 17, carbon atoms or substituted or unsubstituted aralkyl
with 8 to 20 carbon atoms and preferably 10 to 18 car
(NI-12);;
y being an integer from 1 to 3,
(b)
bon atoms, R’ and each R" being hydrogen or alkyl,
alkoxy (also in the form of ethylene oxide condensation
products), alkylol, alkenyl or acyl, aralkyl or cycloalkyl,
R’
_
-Go—l\.lI.CH2.c1n—N
/
R!
60 and x an integer from 1 to 3;
each R’ being hydrogen, alkyl, alkenyl, alkylol, aralkyl
(4)
or cycloalkyl,
/R!!
—N-— (0th) .—N
\
I
R-C
N-Cllg
%
.2IIF
65
I
R!)
wherein R’ as well as each of the two R" may be hy
wherein R is alkyl, acyl or alkenyl with 7 to 19, prefer
3,083,1 43
4
3
Example 2
ably ll—17, carbon atoms or substituted or unsubstituted
aralkyl with 8 to 20 carbon atoms and preferably 10 to
18 carbon atoms, and R’ is hydrogen, or alkyl, alkoxy,
15 m1. methanol are added to
18.5 g. lauryl amine (1,10 mol). Whilst the mixture is
gently stirred
6.0 g. hydro?uoric acid, 40% (‘/10 mol+20%) are in
troduced.
acyl, alkenyl, alkylol, aralkyl or cycloalkyl; and
(4a)
N-OHq
R-C
\N—-CHI
it’
The reaction mixture is heated on a water bath until dis
solution is complete. Further processing is as described
wherein R is an alkyl or alkylol radical of from 9 to 10 in Example 1. The residue is dried in the open air or in
an H2504 desiccator. Lauryl amineHF is a colour
20 carbon atoms, and R’ is alkyl or alkylol.
less, crystalline powder of greasy touch and has the
It has also been found that surface-active compounds
formula
of amphoteric character which are nevertheless capable
CIZHZSNHZHF
of forming salts with hydro?uoric acid and thus exhibit
cation-active properties, reduce the acid solubility of the 15
It is soluble in water, ethanol, and methanol, and the
dental enamel. For instance the fatty acid alkylol amides
aqueous solution foams.
and fatty acid polydialkylol amides are capable of addi
Analogously to cetylamine hydro?uoride and lauryl
tively forming a loose bond with hydro?uoric acid.
amine hydro?uoride any of the following compounds
These HF addition compunds are distinguished from the
basic substance without the HF by their greater solubility 20 can be prepared, viz. myristylamine.HF, stearylamine.HF,
decanolamine.HF, hexadecanolamineHF, octamethylene
in water. They are soluble in methanol and ethanol.
diamine.HF or .ZHF, dodecamethylenediamine.HF or
Such compounds correspond to the following general
2HF, dodecylamine.HF, octadecenylamineHF, myristox
yamineHF, l.6.lZ-triaminododecaneBHP.
formulae:
(5)
R—CO—NlI—CII¢—-CII.OII.IIF
25
I
wherein R is alkyl or alkenyl with 7 to 19, preferably
Example 3
38.1 g. diethylamino-ethyl stearylamide (1,10 mol) are
11 to 17, carbon atoms or substituted or unsubstituted
dissolved at the boil under re?ux in
aralkyl with 8 to 20 carbon atoms and preferably 10 to
50 ml. ethanol. At a temperature of about 30° C.
30 6.0 g. hydro?uoric acid, 40%, (1,10 mol+20%) are added
18 carbon atoms, and R’ is hydrogen or a lower alkyl.
to the solution and the whole is then evaporated on a
water bath until its consistency is paste-like.
The
residue is dried in the open air.
The hydro?uoride of the formula
I
C17H35C O—NII——CI[¢—~G H2~N
wherein R is alkyl or alkenyl with 7 to 19, preferably
11 to 17, carbon atoms or substituted or unsubstituted
aralkyl with 8 to 20 carbon atoms and preferably 10 to
18 carbon atoms, and R’ is hydrogen or a lower alkyl.
The novel compounds according to the invention can
/Czl.l5.n F
C2115
40
is soluble in water, ethanol and methanol. It is colour
less and of waxy consistency. The aqueous solution has
good foam forming properties.
be prepared by reacting the bases, either dry, or in solu
Example 4
tion or suspension in suitable media such as methanol,
ethanol, etc., with aqueous hydro?uoric acid or gaseous 45
37.9 g. diethylamino ethyl oleylamide (V10 mol) are dis
hydrogen ?uoride to form salts therewith, and by then
solved in
carefully evaporating the solvent (if any). The hydro
50 ml. ethanol.
?uoride is obtained in the form of a suspension it is
6.0 g. hydro?uoric acid, 40% (1/10 mol+20%) are added
separated by ?ltration. In the case of compounds which
to the solution and the solvent is largely evaporated on
show little tendency to bind HF additively the former are 50
a water bath. The remaining solvent is driven out of
brie?y heated without solvent with the stoichiometric
the oily residue in vacuo at about 50° C.
quantity of aqueous hydro?uoric acid and without re
The hydro?uoride of the ‘formula
moving the water an aqueous ?nal product is obtained
after cooling.
Calf;
Presently-preferred groups are as hereinafter claimed; 55
and the preparation of preferred embodiments of the
invention are illustrated in the following representative
.IIF
C all;
examples, wherein “ml.” signi?es milliliters, and “g.” sig
ni?es grams. Percentages are by weight.
is a slightly brownish discoloured oil, soluble in water,
60 ethanol and methanol.
Example 1
20 ml. methanol are added to
24.1 g. cetyl amine (1A0 mol) and 6.0 g. 40% hydro?u
The aqueous solution foams.
Instead of the hydro?uorides mentioned in Examples 3
and 4 any one of the following compounds can be prepared
in an analogous way, viz. diethylaminoethyl octoyl
are then introduced.
amide.HF, diethanolamino—ethyl stearoylamide.HF, do
decanolamino-ethyl oleylamide.HF, oleylamino-ethyl my
has completely dissolved. When the solvent is evapo
rated a paste-like residue remains, which is brie?y dried
ristylamide.HF, di-isopropylamino-ethyi lauroylamide.
oric acid
(l/m molt-20%)
The mixture is heated on a Water bath until the amine 65
HF.
olf in a vacuum at 50 to 60° C.
Example 5
The acetyl amine hydro?uoride thus obtained has the 70 15 ml. water and then
formula
10 g. hydro?uoric acid, 40% (310 mol) are added to
CMHSBNHZHF
44.4 g. vdiethanolaminopropyl-N’-ethanol-octadecylamine
and is in the form of a colourless, crystalline powder
1/10 mol). The paste-like reaction compound is
which is greasy to the touch.
It is soluble in water,
methanol, and ethanol, and the aqueous solution foams. 75
kneaded until homogeneous and then dried over desic
cating agents or in the open air.
3,083,143
6
5
remains as a colourless slightly yellowish paste. It is
soluble in ‘water, ethanol, and methanol. The aqueous
solution foams.
Analogously, the following hydro?uorides can be pre
The resultant hydro?uoride of the formula
pared, viz. octoyl ethanolamide.HF, lauroyl isopropanol
amide.HF, palmitoyl ethanolamide.HF, oleyl ethanol
amide.HF, oleyl monoisopropanolamideHF, stearoyl di
isopropanolamide.I-IF, myristoyl diethanolamide.HF.
In a similar way as that described in the above ex
is soluble in water, ethanol, and methanol. The aqueous
solution foams.
10 amples anyone of the following compounds can for in
stance be produced, namely co-phenyl decylaminel-IF, co
Analogously any one of the following hydro?uorides
can be prepared, viz. diethanolamino~ethyl-N'-ethanol
toluyl octadecyiamine.HF, stearoyl aminoethyl dibenzyl
amine.HF, lauroyl aminoethyl furfurylamine.HF, N-octa
decenyl-N-(ethylol)-N’-phenylethyl propylene diamine.
octadecenylamine.2HF, diethanolamino-propyl - N’ - etha
nol-octylamine, di - isopropanolamino-ethyl - N’ - methyl
laurylamine.2HF, oleylamino~ethy1-N'-isopropyl myristyl
15
amine.2HF.
The corresponding acylamino compounds may be ob
tained according to conventional methods e.g. by acylat
stance acetylamino-ethyl-N'-ethyl-octadecylamine.HF can
be prepared.
propylene diamine of the formula:
benzyl-Z-dodecyl imidazoline.2HF, l-ethylol-2-(phenyl
hexadecyl)-imidazoline.2HF, co-phenyl stearoyl ethanol
amide.HF, co-phenylmyristoyl diethanolamideHF and the
like.
The efficacy of the novel compounds according to the
invention in inhibiting the solubility of dental enamel
was established by the following tests.
ing or benzoylating of the corresponding amines with fatty
acid anhydrides or fatty acid halides. In this way for in
Example 6
43.8 g. (1,!30 mol) of N-dialkoxy-N'-alkoxydodecyl
ZHF, N-dodecyl-N'-cyclohexyl ethylene diamine.2HF, 1
The roots as well as any spots affected by caries of
otherwise sound teeth (molars and pre-molars) were
25 covered with wax. Having been thus prepared the teeth
were immersed for 20 hours in the active substance which
it was desired to test at a pH of 2.9. The latter had a
?uorine concentration of 0.1% F. The surface of the
C1=H95—N—CHz-CH:-CIh-N
teeth was well rinsed in distilled water and then decalci?ed
( Hg-CIl'rOhH
(Clh-CIlz-Ohll
30 in a phthalate buffer solution having a pH of 4.0. This
are dissolved in 200 g. of methanol and to the resultant
was performed whilst shaking for 3 hours at 37° C.
solution is added 2.95 g. of aqueous hydro?uoric acid,
The calcium and phosphorus dissolved out of the teeth
38%, i.e. 1,50 mol thereof plus an excess amount of 10
was quantitatively determined in the decalcifying solu
percent. The solvent is then distilled off from the reac
tion. The calcium determination was complexometrically
tion solution and the residue dried in vacuo.
performed by Schwarzenbach‘s method, and the phos
(cni-cniomr
In an analogous way also lower and higher alkoxy
condensation products can be prepared instead of the
phorus was determined colormetrically according to
Fiske and Subbarow. The results provided a direct meas—
ure of the solubility of the enamel and hence of the ef?
cacy of the tested substance. Sodium chloride was used
40 as a reference substance without protective effect. The
10 ‘ml. water are added to
results were therefore all referred to this substance. A
37.8 g. 1~ethanol-2-oleylimidazoline (V10 mol).
series of comparative tests performed as described with
10.0 g. hydro?uoric acid, 40% (-310 mol) are then added
NaCl and the substances enumerated in Examples 1 to
progressively. The initially oily base stiffens as salt
8 disclosed decreases of solubility of the enamel as set
formation proceeds under heat. The crumbly mass is 45 forth in the following table.
above alkoxy derivative.
Example 7
kneaded to homogeneity.
Drying can be performed
in a sulphuric acid desiccator or in the open air.
In percent In percent
The hydrofluoride of the formula
for
calcium
N-CHa
01111330 0-0
/
-2HF
50
NaCl ________________________________________ _-
0
0
90
93
Substance Example:
N--- H:
1 _ __ _ __ . _
_ _ _ _ _
tJJIIi-CIhO H
is soluble in water, ethanol and methanol. The aqueous
solution foams.
Analogously the following hydro?uorides can be pre
pared as described in Example 6, viz.
for
phosphorus
_ _ . _ _ _ . _ . __
86
89
72
61
83
86
69
66
84
B5
74
83
l-ethanol-Z-hepta
decylimidazoline.2HF, 1-ethyl-2-pentadecenyl-imidazoline.
ZHF, 1-isopropanol-Z-tridecyl-imidazoline.2HF, l-rnethyl
2-undecylirnidazoline.ZHF, 1-dodecyl-Z-nonylimidazoline.
2HF, Z-heptadecenylimidazoline.ZHF, l-oleyl-2-octade
cylimidazoline.HF, 1-acetyl-2-dodecylimidazo1ine.HF, l
aethyl-2-undecoxy-imidazoline.2HF.
Example 8
30.2 g. lauroyl-diethanolamide, 95%, (1A0 mol) are heated
Apart from the mentioned novel active substances,
preparations according to the invention for the care of
60 teeth may contain the usual abrasives, such as calcium
phosphate, calcium carbonate, magnesium carbonate,
calcium sulphate, insoluble precipitated alkaline earth
?uorides, kaolins, bolus, etc. However, it has been found
that, owing to the presence of these ingredients, some of
65 the ?uorine is prevented from taking the desired effect
by forming insoluble alkaline earth ?uorides or by being
retained by adsorption.
on a water bath and
5.0 g. hydro?uoric acid, 40% (1A0 mol) are added thereto.
It was further found that the oxides, ortho- and pyro
phosphates, of tin and zinc are outstandingly useful ab
geneous melt is obtained which is then allowed to cool. 70 rasives in dentri?ces.
Heating is continued for a short time until a homo
The hydro?uoride of the formula
ctn-ornorr
oumtc O-N
The present invention therefore also relates quite gen
erally to preparations for the care of the teeth which, in
addition to the conventional ingredients, contain an oxide,
an ortho-, or pyrophosphate, of tin or zinc.
Since it
75 was found that the oxides, the ortho- and pyrophos
3,083,143
8
phates, of tin and zinc, leave a much larger quantity of
should be 0.01 to 4%, preferably between 0.05 to 1%.
the ?uorine available in reactive form, the above men
tioned oxides and/or phosphates are particularly suitable
The powdered fruit kernels or cellulose ethers are dis
solved in part of the water to form a mucilage and the
active reagent dissolved in the remainder of the water
for incorporation in any ?uorine-containing dental prep
aration which contains one of the ?uorine compounds
previously proposed. However, the said oxides and/or
is then added. Finally, the glycerine, aroma, abrasive,
and possibly the wetting and/or foaming agent, are in
phosphates are particularly suitable as additives to the
novel ?uorine compounds proposed by the invention and
in combination with them their effect for the conservation
of teeth is excellent.
10
Furthermore, the dental preparations according to the
Example 12
For instance, a mouth wash may have the following
invention may contain additional surface-active substances
composition:
with a foaming and wetting action, as well as aroma-pro~
viding agents and ?avours.
corporated. The mixture is thoroughly mixed in a suit
able mixing machine and if necessary homogenised in a
rolling or colloid mill.
With reference to the ?rst
Percent
group, care must be taken to see that a combination with
Ethyl
anion-active substances does not signi?cantly reduce the
effect of the cation-active substances proposed by the
Glycerine _________________________________ __
15.0
Aroma (oil of Wintergreen) __________________ __
5.0
invention.
alcohol ______________________________ __ 58.8
Diethylamino ethyl stearylamide
It is therefore preferred to use wetting and
foaming agents exhibiting no ionogenic activity.
In paste-like preparations mucilages and swelling agents
hydro?uoride
_____________ __ 21.2 corr. with 1% F.
Before use the preparation is considerably diluted, for
instance in the proportion of 2 ml. per 50 ml. of water,
so that the concentration in application is 0.04% F.
The active agent is dissolved in the ethyl alcohol with
the application of heat, the aroma and glycerine being
added after the solution has cooled.
Example 13
of an organic or inorganic nature as well as softeners,
such as glycerine, sorbitol syrup, glucose syrup, may be
incorporated. In the selection of suitable mucilages it
has been found that a large number of cation-active
reagent containing the usual mucilage-forming ingredients,
such as tragacanth, alginate, carboxymethylcellulose, car
rageen, are incompatible to a more or less marked de
gree. It is preferred to use mucilages prepared from the
seed kernels of fruits, cellulose ethers or the like.
A tooth powder may have the following composition:
Percent
Liquid dental preparations consist of an aqueous or 30
principally aqueous-alcoholic solution of the compounds
Zinc pyrophosphate _________________________ __ 95.4
proposed by the invention with the usual additives, such
as ?avours, aromatic agents, non-ionogenic emulsi?ers,
and wetting agents, glycerine, sorbitol syrup, and drug
Non-ionogenic emulsi?er, viz. polyoxyethylene sor
Lauryl amine hydro?uoride_____ 1.1 corr.with 0.1% F.
Aroma (oil of peppermint) __________________ __
1.0
extracts, to the extent they are compatible.
bitane
A number of exemplary dentifrices, such as tooth-pastes
and powders, and mouth washes are given hereunder by
way of non-limiting illustrations (“corr.”:correspond
The ?nely powdered dry ingredients are well mixed
ing to):
Example9
monostearate _______________________ __
2.5
in a suitable mixer and the aroma component is slowly
added during the mixing process.
The active compounds employed in the above Exam
40 ples 9 to 13 be replaced by others of the general formula
A toothpaste may have the following composition:
Percent
Moreover, the ?llers and carrier materials, abrasives,
Zinc ortho-phosphate _______________________ __
35.0
emulsi?ers, solvents, and so forth, may be varied as de
Sorbitol syrup _____________________________ __
15.0
Powdered fruit kernels _____________________ -_
1.0
sired and suitable other ?uorine compounds according
to the invention substituted for those mentioned above
to prepare tooth pastes, mouth washes, and tooth pow
ders of other compositions.
The mouth washes and dentifrices according to the
Aroma (oil of Wintergreen) _________________ __
1.0
Cetyl amine hydro?uoride ________ __ 1.37 corr. 0.1% F.
Water ___________________________________ __ 46.63
50 invention may alternatively be prepared by performing
Example 10
A dentifrice may have the following composition:
the reaction of the hydro?uoric acid with the base com
ponents in the course of preparation of the dentifrices
and so forth, principally in the case of the pastes and
washes. To this end the base component is dissolved
or suspended in part of the liquid ingredients, heated if
necessary, and reacted by the careful addition of aque
ous hydro?uoric acid to the cation-active compound. The
Percent
Tin (IV) oxide _____________________________ __ 40.0
Glycerine _________________________________ __
12.0
Methyl cellulose ____________________________ __
1.0
Aroma (oil of peppermint) _________________ __
1.0
remaining ingredients are added subsequently.
l-ethoxy-2-oleylimidazoline hydro?uo
The method may be illustrated by the following non
ride ________________________ __ 1.1 corr. 0.1% F.
Water ____________________________________ __ 44.9
60
Example I 4
Example 11
A tooth paste:
Percent
Percent
Slurry of powdered fruit kernels ______________ __ 60.0
Titanium dioxide ___________________________ __
1.0
Glycerine _________________________________ __
12.0
Saccharine
limiting examples.
________________________________ __
0.1
Aroma (oil of peppermint) __________________ __
1.5
Zinc ortho-phosphate ________________________ __ 40.0
Glycerine _________________________________ __ 15.0
Powdered fruit kernels ______________________ __
1.0
Diethanolamino-propyl-N’-ethanol octa
decylamine dihydro?uoride (5.5% of
70
?uorine) _____________________ __ 3.6 corr. 0.2% F.
Aroma (oil of Wintergreen) __________________ __
1.5
Diethyl amino ethyl oleylamide _______________ __
3.1
Hydro?uoric acid, 20% ______________________ __
0.8
Water ____________________________________ _.. 38.6
The pH values of the aforementioned pastes should be
within the range 3.5 to 7, preferably between 3.8 to 5.5.
The base is dispersed in half the total quantity of water
and the hydro?uoric acid is added slowly while the sus
pension is stirred. To complete the reaction the tem
perature is subsequently raised to 60° C. After the solu
The proportion of active substance, calculated as fluorine,
tion has cooled the mucilage is incorporated. The latter
Water ____________________________________ __
21.8
3,083,143
hydrogen, alkyl, allrenyl, alkylol, aralkyl and cyclo
alkyl radicals;
is prepared by dissolving the powdered fruit kernels in the
rest of the water. The glycerine and the aroma are then
each of R’, R" and R'" is a member selected from the
added and ?nally the zinc ortho-phosphate is incorporated
whilst the mixture is continuously stirred. It is preferable
to homogenise the paste in a homogenising mill.
Example 15
A mouth wash:
group consisting of hydrogen, alkyl, alkoxy, alkylol,
alkenyl, acyl, aralkyl and cycloalkly radicals;
R’”’ is a member selected from the group consisting
of hydrogen, alkyl, acyl, alkenyl, alkylol, aralkyl and
cycloalkyl radicals;
\ Percent
R* is a member selected from the group consisting of
Dodecanol amine __________________________ __ 15.85
Ethyl alcohol _____________________________ __ 68.99
Hydro?uoric acid, 40% ____________________ __
Aroma (oil of Wintergreen) ________________ __
sweetening agent (saccharine) _______________ __
3.95
1.20
0.01
Water ___________________________________ __
10.0
10
With the application of a little heat the amine is dis
solved in the ethyl alcohol. The hydro?uoric acid is added
slowly when the solution has cooled whilst stirring. The
mixture heats up and when it has cooled again the aroma
hydrogen and lower alkyl radicals;
R1 is an alkylene radical of from about 8 to about 20
carbon atoms;
R2 is a member selected from the group consisting of
alkyl and alkenyl radicals of from about 8 to about
20 carbon atoms;
R3 is a member selected from the group consisting of
alkyl, alkoxy, acyl, alkenyl, alkylol, aralkyl and cy
cloalkyl radicals; and
z is a positive integer of at most two; and
and then the water and the sweetening agent are added. 20 (B) the abrasive leaves a substantial quantity of the ?uo
The concentration of active agent in the preparation
rine available in reactive form.
3. A dentifrice composition comprising a caries prophy
is equivalent to 1.5% ?uorine. The preparation is com
lactic and an abrasive wherein (A) the caries prophylactic
siderably diluted before use, for instance by the addition
of the formula
of 50 ml. water per each ml. preparation, so that the F
concentration for application is 0.03%.
25
It will be understood that the aroma ingredients, sweet
ening agents, ?avoring agents, etc. may be varied as de
R-Nm-HF
wherein R is an alkyl radical of from about 8 to about 20
carbon atoms and (B) the abrasive leaves a substantial
sired, these being essentially conventional per se.
quantity of the ?uorine available in reactive form.
Having thus disclosed the invention, what is claimed is:
4. A dentifrice composition comprising a caries prophy
l. A method of reducing the acid solubility of teeth 30
lactic and an abrasive wherein (A) the caries prophylactic
which comprises applying thereto a surface-active hydro
is an amine hydro?uoride of the formula
?uoride of a cationic organic amine.
2. A dentifrice composition comprising a caries pro
phylactic and an abrasive wherein (A) the caries pro
phylactic is a surface active organic amine hydro?uoride 35 wherein R is an alkylol radical of from about 8 to about
20 carbon atoms and (B) the abrasive leaves a substantial
selected from the group consisting of those of the for
quantity of the ?uorine available in reactive form.
mulae:
5. A dentifrice composition comprising a caries prophy
lactic and an abrasive wherein (A) the caries prophylactic
40 is an amine hydro?uoride of the formula
wherein R is an alkylene radical of from about 8 to about
20 carbon atoms and (B) the abrasive leaves a substantial
quantity of the ?uorine available in reactive form.
6. A dentifrice composition comprising a caries prophy
lactic and an abrasive wherein (A) the caries prophylactic
is an amine hydrotluoride of the formula
50
wherein R is a member selected from the group consisting
of alkyl and alkenyl radicals of from about 7 to ‘about 19
55 carbon atoms, and R’ is a member selected from the group
consisting of hydrogen, lower alkyl, alkenyl, alkylol,
aralkyl and cycloalkyl radicals; and (B) the ‘abrasive
leaves a substantial quantity of the ?uorine available in
reactive form.
60
7. A dentifrice composition comprising a caries prophy
lactic and an abrasive wherein (A) the caries prophylactic
is an amine hydro?uoride of the formula
65
R is a member selected from the group consisting of
alkyl, alkoxy, alkenyl, alkylol and aralkyl radicals
of from about 8 to about 20 carbon atoms;
x is a positive integer of at most three;
y is a positive integer of at most three;
R'1 is a member selected from the group consisting of 75
wherein R is a member selected from the group consisting
of alkyl and alkenyl radicals of from about 8 to about 20
carbon atoms; R’ is a member selected from the group
consisting of alkyl, alkoxy, acyl, alkenyl, alkylol, aralkyl
and cycloalkyl radicals; each R" is a member selected
from the group consisting of hydrogen, alkyl, alkoxy, acyl,
alkenyl, alkylol, aralkyl and cycloalkyl radicals; x is a
positive integer of at most 3; and y is a positive integer
3,083,143
11
12
of at most 2; and (B) the abrasive leaves a substantial
quantity of the ?uorine available in reactive form.
8. A dentifrice composition comprising a caries prophy
lactic and an abrasive wherein (A) the caries prophylactic
15. A dentifrice composition comprising a caries pro
phylactic and an abrasive wherein (A) the caries prophy
lactic is an amine hydro?uoride of the formula
is dicthanolaminopropyl - N’ - ethanol - octadecylamine -
dihydro?uoride and (B) the abrasive leaves ‘a substantial
quantity of the ?uoride available in reactive form.
9. A dentifrice composition comprising a caries prophy
lactic and an abrasive wherein (A) the caries prophylactic
is cetyl amine hydro?uoride and (B) the ‘abrasive leaves 10 wherein R is a member selected from the group consisting
a substantial quantity ‘of the ?uoride available in reactive
form.
10. A dentifrice composition comprising a caries pro
phylactic and an abrasive wherein (1A) the caries prophy
of alkyl and alkylol radicals of from about 9 to about 20
carbon atoms and R’ is a member selected from the group
consisting of alkyl and alkylol and (B) the abrasive leaves
lactic is 1-ethoxy-Zaoleylimidazoline hydro?uoride and 15
(B) the abrasive leaves a substantial quantity of the ?uo
ride available in reactive form.
11. A dentifrice composition comprising a caries pro
phylactic and an ‘abrasive wherein (A) the caries prophy
lactic is lauryl amine hydro?uoride and (B) the abrasive
leaves a substantial quantity of the ?uoride available in
reactive form.
12. A dentifrice composition comprising a caries pro
phylactic and an abrasive wherein (A) the caries prophy
(1B) the abrasive leaves a substantial quantity of the ?uo
ride available in reactive form.
13. A dentifrice composition comprising a caries pro
phylactic and an abrasive wherein (A) the caries prophy
30
lactic is an amine hydro?uoride of the formula
R~NH2'HF
wherein R is an alkylol radical of from about 10 to about
16 carbon atoms and (B) the abrasive leaves a substantial
quantity of the ?uorine available in reactive form.
35
14. A dentifrice composition comprising a caries pro
phylactic and an abrasive wherein (A) the caries prophy
lactic is a surface active organic amine hydro?uoride of
the formula
R-NHQ-HF
quantity of the ?uorine available in reactive form.
_
References Cited in the ?le of this patent
UNITED STATES PATENTS
lactic is diethyl amino ethyl oleylamide hydro?uoride and 25
wherein R is an alkenyl radical of from about 8 to about
20 carbon atoms and (B) the abrasive leaves a substantial
a substantial quantity of the ?uorine available in reactive
form.
2,166,119
2,166,120
2,228,985
2,228,987
2,238,069
2,246,524
Bousquet _____________ __ July
Bousquet _____________ __ July
De Groote ____________ __ Jan.
De Groote ____________ __ Jan.
Miller ______________ __ Apr.
Kyrides _____________ __ June
18,
18,
14,
14,
15,
24,
1939
1939
1941
1941
1941
1941
2,361,524
2,362,614
2,472,361
2,541,088
2,565,189
2,590,073
Allardt _______________ __ Oct. 31,
Calva _______________ __ Nov. 14,
Arsem ________________ __ June 7,
Nikowitz ______________ __ Feb. 13,
Wernlund ___________ __ Aug. 21,
Albrecht ____________ __ Mar. 25,
1944
1944
1949
1951
1951
1952
2,644,826
Spivak _______________ __ July 7, 1953
2,680,137
2,692,264
2,749,278
Pickett _______________ __ June 1,
Wojcik ______________ __ Oct. 19,
Moss _________________ _._ June 5,
Garmaise ____________ __ May 14,
Winthrop ____________ __ Nov. 12,
Wessinger ____________ __ Dec. 31,
De Benneville _________ __ Jan. 21,
2,792,404
2,813,102
2,818,371
2,820,801
40
1954
1954
1956
1957
1957
‘1957
1958
FOREIGN PATENTS
207,489
543,066
‘ I a
s
Australia _____________ __ Apr. 17, 1957
Canada _______________ __ July 2, 1957
13
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,083§l43
March 26, 1963
Hans Schmid et al.
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 38, after "of" insert —— a fluoride of —~;
column 2, lines 3 to 7V the formula should appear as shown below
instead of as in the patent:
I
same column 2, line 36, the formula should appear as shown below
instead of as in the patent:
R—(NH2)X.yHF
column Ll, lines 55 to 58, the formula should appear as shown
below instead of as in the patent:
2 5
C17H33CO—-NH-CH2—C?2-~N
,HF
C2H5
column 10,
line 23, after "prophylactic" insert —— is an amine
hydrofluoride ——.
Signed and sealed this 24th day of December 1963.
(SEAL)
Attest:
ERNEST W. SWIDER
EDWIN L, REYNOLDS
Attesting Officer
Acting Commissioner of
Patents
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,083, 143
March 26, 1963
Hans Schmid et al.
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 38,
after "of" insert —— a fluoride of ——;
column 2, lines 3 to 7, the formula should appear as shown below
instead of as in the patent:
/N__CH2
/ l
\IT—CH2
R
same column 2, line 36, the formula should appear as shown below
instead of as in the patent:
column 4, lines 55 to 58, the formula should appear as shown
below instead of as in the patent:
'C2H5
Cl7H33CO—NH—CH2—CH2—N
.HF
C2H5
column 10,
line 23, after "prophylactic" insert -— is an amine
hydrofluoride ——-.
Signed and sealed this 24th day of December 1963.
(SEAL)
Attest:
ERNEST W. SWIDER
Attesting Officer
EDWIN L. REYNOLDS
Ac ting Commissioner of
Patents
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