Note: Descriptions are shown in the official language in which they were submitted.
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BETAINE ESTER COMPOUNDS OF ACTIVE ALCOHOLS
Field of the invention
The present invention relates to betaine ester compounds of active alcohols.
15 More particularly, it relates to stabilised betaine ester compounds of activealcohols in an acidic environment such as in a fabric softener composition.
Background of the invention
Cleaning and laundry products are well known in the art. However,
consumer acceptance of cleaning and laundry products is determined not
only by the performance achieved with these products but also the
25 aesthetics associated therewith. The perfume components are therefore an
important aspect of the successful formulation of such commercial
products.
Accordingly, formulations of compounds which provide a slow release of
30 the perfume over a longer period of time than by the use of the perfume
itself have been provided. Disclosure of such compounds may be found in
WO 95/04809, WO 95/08976 and pending application EP 95303762.9.
Pending application EP 95303762.9 describes betaine ester compounds of
perfume alcohols which provide release of the perfume components over a
35 long period of time.
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Although betaine ester compounds are effective in the slow release of
perfume, it has now been found that in an acidic environment such as in
acidic product, the described compounds hydrolyse upon storage to release
their perfume component, therefore reducing the amount of perfume alcohol
5 released upon and after the washing or cleaning process. By acidic
environment, it is meant a pH value of less than 7Ø
The formulator of a laundry and/or cleaning compositions is thus faced with
the challenge of formulating a compound which is stable in an acidic
10 environment but which still produces a slow release of the active alcohol
~e.g perfume) upon and after the washing or cleaning process.
The Applicant has now found that the provision of betaine ester compounds
of active alcohols in combination with a surfactant, wherein said betaine
esters at a concentration of from 0.01% to 10% by weight are
predominantly in the form of micelles, and/or are capable of being
incorporated into micelles, overcomes the problem. Preferably, said betaine
esters have at least one long alkyl chain.
20 Therefore, the present invention encomp~sses acidic compositions
comprising betaine ester compounds of active alcohol components having a
long alkyl chain, which at a concentration of from 0.01% to 10% by weight
are predominantly in the form of micelles, and/or are capable of being
incorporated into micelles, in cG",bination with a surfactant. For optimum
25 benefit of storage stability and slow release of the active alcohol upon and
after the washing or cleaning process, a cationic surfactant is preferred.
Not to be bound by theory, it is believed that the use of betaine ester
compounds with at least one long alkyl chain provide said betaine esters
30 with a hydrophobic character which enable them to be rearranged in micelle
form and/or to be incorporated into micelles, thereby protecting the ester
bond from hydrolysis by the acidic environment.
For the purpose of the invention, the term "acidic aqueous composition"
35 includes compositions having a pH value below or equal to 7.0, whereby
the pH is measured at 20~C in the neat liquid product .
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By "slow release" is meant release of the active component ~e.g perfume)
over a longer period of time than by the use of the active (e.g perfume)
itself .
Accordingiy, the slow release concept and storage stability advantage of
5 the invention may be applied to other active alcohol components such as a
flavour alcohol ingredient, a pharmaceutical alcohol active or a biocontrol
alcohol agent and any other active alcohol component where a slow release
of said active component is necessary.
Summarv of the invention
The present invention relates to an aqueous acidic composition comprising
15 a~ a betaine ester of an active alcohol which, at a concentration of from
0.01% to 10% by weight, is predominantly in the form of micelles,
and/or is capable of being incorporated into micelles, and
b) a surfactant,
said composition comprising an acidic material in sufficient amount to
20 render the pH of the composition of less than 7.
In a preferred embodiment of the invention, the betaine ester is a
hydrophobic betaine ester of formula:
R1 + R ~
R2--N ~C3~C--OR
R3 R'2 ~
wherein each R1, R2, R3 independently, is selected from hydrogen, alkyl
group, aryl group,
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WO 97/36978 4 PCT/US97104959
r 1
LCH2Jn
R 1 . R', + Rl1
rC~o R R ~ RO--C C--N~C-~C--OR
R n3 { 3~ o 2 R~ 2
and
- R1- R~ R'1
(CH2)n1 - + ~J (CH2)n1--N~C}~C--OR (n2 +1)A -
R2- n2 I R'2 ~
and with the proviso that where each R1, R2 and R3, independently, are
only selected from hydrogen, aryl or alkyl groups, then at least one of R1,
R2 or R3 is an alkyl or aryl group having at least 8 carbon atoms,
wherein R4 is an alkyl group having from 7 to 19 carbon atoms,
wherein each R' 1, R'2, independently, is selected from hydrogen, alkyl
group, aryl group, -CH2-COOH, -CH2-COOR, -CH2-CH2-COOH and -CH2-
CH2-COOR,
wherein each n, n1, independently, is an integer Iying in the range from 1 to
20, and
wherein n2 is an integer Iying in the range of O to 20,
wherein each n3, independently, is an integer Iying in the range from 1 to 3,
and wherein each R, independently, is an organic chain of an active alcohol.
In another aspect of the invention a process for preparing said acidic
composition is provided, whereby said process further improves the betaine
ester protection from the acidic environment. A typical process for
preparing a composition containing a surfactant comprises the following
steps:
- mixing the surfactant and optional components, if any, at a temperature
above the melting point of the surfactant,
- preparing a waterseat,
- dispersing the mixture prepared above in the waterseat, and
- optionally, cooling the resulting dispersion.
Protection of the betaine ester occurs by incorporation of said betaine ester
with the molten surfactant, or prior to dispersion of the molten surfactant in
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a waterseat, or with the surfactant dispersion while the dispersion is at a
temperature above the Krafft point of the surfactant or combination of any
of the above.
Detailed descriotion of the invention
Betaine ester comDounds of active alcohols
10 An essential component of the invention is a betaine ester of an active
alcohol, which, at a concentration of from 0.01% to 10% by weight in
said composition, is predominantly in the form of micelles, and/or is capable
of being incorporated into micelles, e.g a micelle can be composed of 100%
betaine esters or mixed betaine esters/surfactants. Preferably, the betaine
15 ester compounds of an active alcohol have the general formula below:
R1 + R'~
R2--N ~C3~C--OR
R3 R' O
wherein each R1, R2, R3 independently, is selected from hydrogen, alkyl
group, aryl group,
A- ''
R'~ R'. + R'~
R~3~ o {Cl,~ C--O R ~C N ~ C 3~ C--OR
and
- R~- R~ R'1
(CH2)n1 + ~--(CH2)n1--N [Cl~C--OR (n2 +1)A -
- R2- n2 R2 R' O
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and with the proviso that where each R1, R2 and R3, independently, are
only selected from hydrogen, aryl or alkyl groups, then at least one of R1,
R2 or R3 is an alkyl or aryl group having at least 8 carbon atoms,
wherein R4 is an alkyl group having from 7 to 19 carbon atoms,
5 wherein each R' 1, R'2, independently, is selected from hydrogen, alkyl
group, aryl group, -CH2-COOH, -CH2-COOR, -CH2-CH2-COOH and -CH2-
CH2-COOR,
wherein each n, n1, independently, is an integer Iying in the range from 1 to
20, and
10 wherein n2 is an integer Iying in the range of O to 20,
wherein each n3, independently, is an integer Iying in the range from 1 to 3,
and
wherein each R, independently, is an organic chain of an active alcohol.
15 Preferably, each n2, independently, is an integer Iying in the range of O to
6.
Preferably, each n3, independently, is an integer of value 1 or 2, more
preferably 1.
Preferably R1, R2, R3 are each, independently selected from H, alkyl chain
having from 1 to 20 carbon atoms, with the proviso that at least one of R1,
R2 or R3 is an alkyl group having at least 8 carbon atoms.
Preferably R'1, R'2 are, each, independently selected from H, alkyl chain
25 having 1 to 3 carbon atoms, phenyl.
For the above mentioned compounds, the R group, which is hydrophobic in
nature, is the organic chain of an active alcohol, said active alcohol being
30 selected from a flavour alcohol ingredient, a pharmaceutical alcohol active, a
biocontrol alcohol agent, a perfume alcohol component and mixtures
thereof. Flavour ingredients include spices, flavour enhancers that
contribute to the overall flavour perception. Pharmaceutical actives include
drugs. Biocontrol agents include biocides, antimicrobials, bactericides,
35 fungicides, algaecides, mildewcides, disinfectants, antiseptics, insecticides,
vermicides, plant growth hormones. Perfume alcohol components include
components having odoriferous properties.
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Preferably, for the above mentioned compounds, the R group is the organic
chain of a perfume alcohol, said alcohol being selected from 2-
phenoxyethanol, phenylethylalcohol, geraniol, citronellol, 3-methyl-5-phenyl-
5 1-pentanol, 2,4-dimethyl-3-cyclohexene-1-methanol, linalool,
tetrahydrolinalool, 1,2-dihydromyrcenol, hydroxycitronellal, farnesol,
menthol, eugenol, vanilin, cis-3-hexenol, terpineol and mixtures thereof.
More preferred R groups, for the purpose of the invention, are selected from
10 the organic chain of a perfume alcohol, said alcohol being selected from
geraniol, citronellol, linalool, dihydromyrcenol and mixtures thereof.
Preferred compounds for the purpose of the invention are selected from
geranyloxycarbonyl-N,N-dimethyl-N-dodecylmethanaminium bromide or
15 chloride; citronellyloxycarbonyl-N,N-dimethyl-N-dodecylmethanaminium
bromide or chloride; linalyloxycarbonyl-N,N-dimethyl-N-
dodecylmethanaminium bromide or chloride; dihydromyrcenyloxycarbonyl-
N,N-dimethyl-N-dodecylmethanaminium bromide or chloride.
20 Other preferred compounds are selected from N-dodecylglycine geranyl
ester hydrobromide or hydrochloride; N-dodecylglycine citronellyl ester
hydrobromide or hydrochloride; N-dodecylglycine linalyl ester hydrobromide
or hydrochloride; N-dodecylglycine dihydromyrcenyl ester hydrobromide or
hydrochloride.
Other preferred compounds are selected from N,N-dioctylglycine geranyl
ester hydrobromide or hydrochloride; N,N-dioctylglycine citronellyl ester
hydrobromide or hydrochloride; N,N-dioctylglycine linalyl ester hydrobromide
or hydrochloride; N,N-dioctylglycine dihydromyrcenyl ester hydrobromide or
30 hydrochloride.
Other preferred compounds are selected from N,N-didodecylglycine geranyl
ester hydrobromide or hydrochloride; N,N-didodecylglycine citronellyl ester
hydrobromide or hydrochloride, N,N-didodecylglycine linalyl ester
35 hydrobromide or hydrochloride; N,N-didodecylglycine dihydromyrcenyl ester
hydrobromide or hydrochloride.
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Other preferred compounds are seiected from N-(2-geranyloxy-2-oxoethyl~-
N,N-dimethyl-2-geranyloxy-2-oxoethanaminium bromide or chloride; N-t2-
5 citronellyloxy-2-oxoethyl)-N,N-dimethyl-2-citronellyloxy-2-oxoethanaminium
bromide or chloride; N-(2-linalyloxy-2-oxoethyl)-N,N-dimethyl-2-linalyloxy-2-
oxoethanaminium bromide or chloride; N-(2-dihydromyrcenyloxy-2-
oxoethyl)-N,N-dimethyl-2-dihydromyrcenyloxy-2-oxoethanaminium bromide
or chloride.
Other preferred compounds are selected from N-butyl-N-(2-geranyloxy-2-
oxoethyl)glycine geranyl ester hydrobromide or hydrochloride; N-butyl-N-(2-
citronellyloxy-2-oxoethyl)glycine citronellyl ester hydrobromide or
hydrochloride; N-butyl-N-(2-linalyloxy-2-oxoethyl)glycine linalyl ester
15 hydrobromide or hydrochloride; N-butyl-N-~2-dihydromyrcenyloxy-2-
oxoethyl)glycine dihydromyrcenyl ester hydrobromide or hydrochloride.
Other preferred compounds are selected from N-dodecyl-N-(2-geranyloxy-2-
oxoethyl)glycine geranyl ester hydrobromide or hydrochloride; N-dodecyl-N-
20 (2-citronellyloxy-2-oxoethyl)glycine citronellyl ester hydrobromide or
hydrochloride; N-dodecyl-N-(2-linalyloxy-2-oxoethyl)glycine linalyl ester
hyclrobromide or hydrochloride; N-dodecyl-N-(2-dihydromyrcenyloxy-2-
oxoethyl)glycine dihydromyrcenyl ester hydrobromide or hydrochloride.
25 Other preferred compounds are selected from N,N-bis(2-geranyloxy-2-
oxoethyl)glycine geranyl ester hydrobromide or hydrochloride; N,N-bis(2-
citronellyloxy-2-oxoethyl)glycine citronellyl ester hydrobromide or
hydrochloride; N,N-bis(2-linalyloxy-2-oxoethyl)glycine linalyl ester
hydrobromide or hydrochloride; N,N-bis(2-dihydromyrcenyloxy-2-
30 oxoethyl)glycine dihydromyrcenyl ester hydrobromide or hydrochloride.
Mixtures of any of the above components in the betaine ester used herein inthe compositions of the invention may be used.
35 Preferably, levels of incorporation of said betaine ester compounds of active alcohols, into the acidic composition are from 0.01% to 8%, more
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preferably 0.05% to 5%, and most preferably from 0.1% to 2%, by weight
of the total composition.
5 Surfactant
The other essential component of the invention is a surfactant. Such
surfactant are selected from anionic, nonionic, cationic, amphoteric and
zwiterrionic surfactants.
Anionic surfactant
Essentially any anionic surfactants useful for detersive purposes can be
included in the compositions. These can include salts (including, for
15 example, sodium, potassium, ammonium, and substituted ammonium salts
such as mono-, di- and triethanolamine salts~ of the anionic sulfate,
sulfonate, carboxylate and sarcosinate surfactants.
Other anionic surfactants include the isethionates such as the acyl
20 isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinates and sulfosuccinates, monoesters of sulfosuccinate (especially
saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate
(especially saturated and unsaturated C6-C14 diesters~, N-acyl sarcosinates.
Resin acids and hydrogenated resin acids are also suitable, such as rosin,
25 hydrogenated rosin, and resin acids and hydrogenated resin acids present in
or derived from tallow oil.
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol
30 sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-C17 acyl-N-(C1-
C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
nonsulfated compounds being described herein).
35 Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C6-C1g alkyl sulfates which have been ethoxylated with
from about 0.5 to about 20 moles of ethylene oxide per molecule. More
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preferably, the alkyl ethoxysulfate surfactant is a C6-C 18 alkyl sulfate
which has been ethoxylated with from about 0.5 to about 20, preferably
from about 0.5 to about 5, moles of ethylene oxide per molecule.
Anionic sulfonate surfactants suitable for use herein include the salts of
Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22
primary or secondary alkane sulfonates, C6-C24 olefin sulfonates,
sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol
sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic carboxylate surfactants suitable for use herein include the alkyl
ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and
the soaps ('alkyl carboxyls'), especially certain secondary soaps as
described herein. Preferred alkyl ethoxy carboxylates for use herein include
those with the formula RO(CH2CH20)X CH2COO-M + wherein R is a C6 to
C1g alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is
such that, on a weight basis, the amount of material where x is 0 is less
than about 20 %, and the amount of material where x is greater than 7, is
less than about 25 %, the average x is from about 2 to 4 when the
average R is C13 or less, and the average x is from about 3 to 10 when the
average R is greater than C13, and M is a cation, preferably chosen from
alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-
ammonium, most preferably from sodium, potassium, ammonium and
mixtures thereof with magnesium ions. The preferred alkyl ethoxy
carboxylates are those where R is a C12 to C1 8 alkyl group.
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include
those having the formula R0-(CHR1-CHR2-0)-R3 wherein R is a C6 to C1g
alkyl group, x is from 1 to 25, R1 and R2 are selected from the group
consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R1
or R2 is a succinic acid radical or hydroxysuccinic acid radical, and R3 is
selected from the group consisting of hydrogen, substituted or
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and
mixtures thereof .
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Preferred soap surfactants are secondary soap surfactants which contain a
carboxyl unit connected to a secondary carbon. The secondary carbon can
be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-
substituted cyclohexyl carboxylates. The secondary soap surfactants should
5 preferably contain no ether linkages, no ester linkages and no hydroxyl
groups. There should preferably be no nitrogen atoms in the head-group
(amphiphilic portion). The secondary soap surfactants usually contain 1 1-15
total carbon atoms, although slightly more (e.g., up to 16) can be tolerated,
e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred
secondary soap surfactants:
A. A highly preferred class of secondary soaps comprises the secondary
15 carboxyl materials of the formula R3 CH(R4)CooM, wherein R3 is
CH3(CH2)x and R4 is CH3(CH2)y, wherein y can be 0 or an integer from 1
to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably
7-9, most preferably 8.
20 B. Another preferred class of secondary soaps comprises those carboxyl
compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit,
i.e., secondary soaps of the formula R5-R6-CooM, wherein R5 is C7-C10,
preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as
benzene, cyclopentane and cyclohexane. (Note: R5 can be in the ortho,
25 meta or para position relative to the carboxyl on the ring.)
C. Still another preferred class of secondary soaps comprises secondary
carboxyl compounds of the formula
CH3(CHR)k~(CH2)m~(CHR)n~CH(COOM)(CHR)o~(CH2)p~(CHR)q~CH3~
30 wherein each R is C1-C4 alkyl, wherein k, n, o, q are integers in the range
of 0-8, provided that the total number of carbon atoms (including the
carboxylate) is in the range of 10 to 18.
In each of the above formulas A, B and C, the species M can be any
35 suitable, especially water-solubilizing, counterion.
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Especially preferred secondary soap surfactants for use herein are water-
soluble members selected from the group consisting of the water-soluble
salts of 2-methyl- 1 -undecanoic acid, 2-ethyl- 1 -decanoic acid, 2-propyl- 1-
nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (R1) CH2 COOM, wherein R is a Cs-C17 linear or branched
alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal
10 ion. Preferred examples are the myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
Nonionic surfactant
Essentially any nonionic surfactants useful for detersive purposes can be
15 included in the compositions. Exemplary, non-limiting classes of useful
nonionic surfactants are listed below.
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula R2CONR1 Z wherein : R1 is H, C1 -C4 hydrocarbyl, 2-
20 hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferabie C 1 -C4
alkyl, more preferably C 1 or C2 alkyl, most preferably C 1 alkyl (i .e.,
methyl); and R2 is a Cs-C31 hydrocarbyl, preferably straight-chain Cs-C1g
alkyl or alkenyl, more preferably straight-chain Cg-C 17 alkyl or alkenyl,
most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture thereof;
25 and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at
least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will
be derived from a reducing sugar in a reductive amination reaction; more
preferably Z is a glycityl.
The polyethylene, polypropylene, and polybutylene oxide condensates of
alkyl phenols are suitable for use herein. In general, the polyethylene oxide
condensates are preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing from about 6 to
35 about 18 carbon atoms in either a straight chain or branched chain
configuration with the alkylene oxide.
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The alkyl ethoxylate condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide are suitable for use herein. The
alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or secondary, and generally contains from 6 to 22 carbon atoms.
Particularly preferred are the condensation products of alcohols having an
alkyl group containing from 8 to 20 carbon atoms with from about 2 to
about 10 moles of ethylene oxide per mole of alcohol.
The ethoxylated C6-C1 g fatty alcohols and C6-C1 g mixed
ethoxylated/propoxylated fatty alcohols are suitable surfactants for use
herein, particularly where water soluble. Preferably the ethoxylated fatty
alcohols are the C10-C18 ethoxylated fatty alcohols with a degree of
ethoxylation of from 3 to 50, most preferably these are the C12-C18
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl
chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of
from 3 to 30 and a degree of propoxylation of from 1 to 10.
The condensation products of ethylene oxide with a hydrophobic base
formed by the condensation of propylene oxide with propylene glycol are
suitable for use herein. The hydrophobic portion of these compounds
preferably has a molecular weight of from about 1500 to about 1800 and
exhibits water insolubility. Examples of compounds of this type include
certain of the commercially-available PluronicTM surfactants, marketed by
BASF.
The condensation products of ethylene oxide with the product resulting
from the reaction of propylene oxide and ethylenediamine are suitable for
use herein. The hydrophobic moiety of these products consists of the
reaction product of ethylenediamine and excess propylene oxide, and
generally has a molecular weight of from about 2500 to about 3000.
Examples of this type of nonionic surfactant include certain of the
commercially available TetronicTM compounds, marketed by BASF.
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably from about
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10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside,
hydrophilic group containing from about 1.3 to about 10, preferably from
about 1.3 to about 3, most preferably from about 1.3 to about 2.7
saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms
5 can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted for the glucosyl moieties. (Optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose
as opposed to a glucoside or galactoside.~ The intersaccharide bonds can
be, e.g., between the one position of the additional saccharide units and the
10 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula
1 5 R2o~cnH2no)t(glycosyl~x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is
2 or 3; t is from O to 10, preferably 0, and X is from 1.3 to 8, preferably
from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably
derived from glucose.
Fatty acid amide surfactants suitable for use herein are those having the
formula: R6CoN(R7)2 wherein R6 is an alkyl group containing from 7 to 21,
preferably from 9 to 17 carbon atoms and each R7 is selected from the
group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -
(C2H40)XH, where x is in the range of from 1 to 3.
Cationic surfactant
Typical cationic surfactants for the purpose of the invention are those
commonly mentioned as cationic fabric softener actives. Such cationic
fabric softening components include the water-insoluble quaternary-
ammonium fabric softening actives, the most commonly used having been
di-long alkyl chain ammonium chloride.
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Preferred cationic softeners among these include the following:
1 ) ditallow dimethylammonium chloride (DTDMAC);
2) dihydrogenated tallow dimethylammonium chloride;
3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) C12-14 alkyl hydroxyethyl dimethylammonium chloride;
1 1 ) C12-18 alkyl dihydroxyethyl methylammonium chioride;
1 5 1 2) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
1 3) di(tallowoyloxyethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-(2-tallowylamidoethyl)-2-tallowyl imidazolinium
methylsulfate.
16) ditallow imidazoline
17) ditallow imidazoline ester
Also included within the scope of cationic fabric softening components are
the more environmentally-friendly materials, and rapidly biodegradable
quaternary ammonium compounds which have been presented as
alternatives to the traditionally used di-long chain ammonium chlorides.
Such quaternary ammonium compounds contain long chain alk~en)yl groups
interrupted by functional groups such as carboxy groups. Said materials and
fabric softening compositions containing them are disclosed in numerous
publications such as EP-A-0,040,562, and EP-A-0,239,910.
The quaternary ammonium compounds and amine precursors herein have
the formula (I) or (Il), below:
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W O 97/36978 16 PCTrUS97/04959
R3~ R3
\ / + N -(CH2)n-C H ~ X-
+ N -(C ~ ~-Q--T I X R3 Q Q
Rl Tl T2
or
(I) ~Il)
wherein Q is selected from -0-C(0)-, -C(0)-0-, -0-C(0)-0-, -NR4-C(o)-, -
5 C(o)-NR4-;
R1 is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;
R4 is H or Cl-C4 alkyl or C1-C4 hydroxyalkyl;
T1, T2, T3, T4, T5 are independently C1 1-C22 alkyl or alkenyl;
n and m are integers from 1 to 4; and
X~ is a softener-compatible anion.
Non-limiting examples of softener-compatible anions include chloride or
methyl sulfate.
The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11
carbon atoms, preferably at least 16 carbon atoms. The chain may be
straight or branched.
20 Tallow is a convenient and inexpensive source of long chain alkyl and
alkenyl material. The compounds wherein T1, T2, T3, T4, T5 represents
the mixture of long chain materials typical for tallow are particularly
preferred.
25 Specific examples of quaternary ammonium compounds suitable for use in
the aqueous fabric softening compositions herein include:
1 ) N, N-di(tallowyl-oxy-ethyl)-N, N-dimethyl ammonium chloride;
2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
30 3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
- 4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride;
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W0 97/36978 17 PCTIUS97104959
5) N-(2-tallowyl-oxy-2-ethyl~-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl
ammonium
chloride;
6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
i) N-(2-tallowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dimethyl-ammonium
chloride; and
8) 1 ,2-ditallowyl-oxy-3-trimethylammoniopropane chloride;
and mixtures of any of the above materials.
Of these, compounds 1-7 are examples of compounds of Formula (I);
compound 8 is a compound of Formula (Il). Particularly preferred is N,N-
di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the tallow
chains are at least partially unsaturated. The level of unsaturation of the
tallow chain can be measured by the lodine Value (IV) of the corresponding
fatty acid, which in the present case should preferably be in the range of
from 5 to 100 with two categories of compounds being distinguished,
having a IV below or above 25. Indeed, for compounds of Formula ~I) made
from tallow fatty acids having a IV of from 5 to 25, preferably 15 to 20, it
has been found that a cis/trans isomer weight ratio greater than 30/70,
preferably greater than 50/50 and more preferably greater than 70/30
provides optimal concentrability. For compounds of Formula (I) made from
tallow fatty acids having a IV of above 25, the ratio of cis to trans isomers
has been found to be less critical unless very high concentrations are
needed.
Other examples of suitable quaternary ammoniums of Formula (I) and (Il) are
obtained by, e.g.:
- replacing "tallow" in the above compounds with, for example, coco,
palm, lauryl, oleyl, ricinoleyl, stearyl, palmityl, or the like, said fatty acylchains being either fully saturated, or preferably at least partly
unsaturated;
- replacing "methyl" in the above compounds with ethyl, ethoxy, propyl,
propoxy, isopropyl, butyl, isobutyl or t-butyl;
- replacing "chloride" in the above compounds with bromide, methylsulfate,
formate, sulfate, nitrate, and the like.
35 .
In fact, the anion is merely present as a counterion of the positively charged
quaternary ammonium compounds. The nature of the counterion is not
CA 022~0837 1998-10-01
WO 97/36978 18 PC'T/US97/04959
critical at all to the practice of the present invention. The scope of this
invention is not considered limited to any particular anion.
By "amine precursors thereof" is meant the secondary or tertiary amines
5 corresponding to the above quaternary ammonium compounds, said amines
being substantially protonated in the present compositions due to the pH
values.
Other cationic surfactants may also be used in addition to or in alternative
10 to the above mentioned cationic surfactants having fabric softening
properties. This include the monoalkyl ammonium halide such as trimethyl
alkyl ammonium halide (R '-N + (Me)3 X~) such as C 1 6 trimethyl ammonium
bromide or C14 trimethyl ammonium bromide; N-alkyl N,N-dimethyl-N(2-
hydroxyethyl) ammonium ~ R'-N + (Me)2CH2CH2OH X~) and mixtures
15 thereof, and wherein R' is an alkyl chain having at least 8 carbons and X~ is a conteranion as defined herein before.
Preferred among these surfactants are the cationic surfactants, most
preferably the cationic surfactants mentioned above as having fabric
20 softening properties.
Typical levels of said surfactants are from 0.1% to 80% by weight of the
compositions .
25 Acidic material
Acidic materials are essenlial to the stability of the composition of the
invention. Acidity may be provided from the above mentioned betaine ester,
especially with those selected from N-dodecylglycine geranyl ester
30 hydrobromide or hydrochloride; N,N-dioctylglycine geranyl ester
hydrobromide or hydrochloride; N,N-didodecylglycine geranyl ester
hydrobromide or hydrochloride; N-butyl-N-(2-geranyloxy-2-oxoethyl)glycine
geranyl ester hydrobromide or hydrochloride; N-dodecyl-N-(2-geranyloxy-2-
oxoethyl)glycine geranyl ester hydrobromide or hydrochloride; N,N-bis(2-
35 geranyloxy-2-oxoethyl)glycine geranyl ester hydrobromide or hydrochloride;
and/or the cationic su. ractants above mentionned themselves.
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Conventional acidic materials may also be used. Suitable conventional acidic
materials include the bronstead acids as well as the fatty acids. Examples of
suitable acids include the inorganic mineral acids, carboxylic acids, in
particular the low molecular weight (C1-Cs~ carboxylic acids, and alkyl
5 sulfonic acids and mixtures thereof.
Suitable inorganic acids include HCI, H2S04, HN03 and H3P04. Suitable
organic acids include formic, acetic, methylsulfonic and ethylsulfonic acid.
Preferred acids are hydrochloric, phopshoric, formic and methylsulfonic
1 0 acid.
The amount of acidic material should be such that the pH of the
composition is less than 7, preferably from 2.0 to 5.5.
More preferably, where cationic surfactants are used, especially those
15 mentioned as biodegradable fabric softening agents, optimum hydrolytic
stability of these compositions will be obtained when the pH of the
compositions, measured in the neat compositions at 20~C, is in the range
of from 2.0 to 4.5.
20 Typically the amount of acid is from 1% to 30% by weight, preferably 2%
to 30%, most preferably 3% to 15% by weight of the cationic surfactant.
Additional inqredients
25 Additional perfume ingredients may be added to the acidic composition.
When presenl, the composition will comprise up to 5% by weight, more
preferably from 0.1% to 1.5% by weight of additional perfume.
Additional perfumes are those odorous materials that deposit on fabrics or
30 surfaces during the laundry or cleaning process and are detectable by
people with normal olfactory sensitivity. Many of the perfume ingredients
along with their odour corrector and their physical and chemical properties
are given in "Perfume and Flavor chemicals (aroma chemicals)", Stephen
Arctender, Vols. I and ll, Aurthor, Montclair, H.J. and the Merck Index, 8th
35 Edition, Merck & Co., Inc. Rahway, N.J. Perfume components and
compositions can also be found in the art, e.g. US Patent Nos. 4,145,184,
4,1 52,272, 4,209,41 7 or 4,51 5,705.
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A wide variety of chemicals are known for perfume use including materials
such as aldehydes, ketones, esters and the like. More commonly, naturally
occurring plant and animal oils and exudates comprising complex mixtures
of various chemical components are known for use as perfume, and such
5 materials can be used herein. Typical perfumes can comprise e.g.
woody/earthy bases containing exotic materials such as sandalwood oil,
civet and patchouli oil. The perfume also can be of a light floral fragrance
e.g. rose or violet extract. Furthermore, the perfume can be formulated to
provide desirable fruity odours e.g. Iime, lemon or orange.
Particular examples of optional perfume ingredients and compositions are
anetole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso-
bornyl acetate, camphene, cis-citral (neral~, citronellal, citronellol, citronellyl
acetate, paracymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl
15 phenyl carbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl
nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool
oxide, ~inalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl
ionone, methyl nonyl acetaldehyde, methyl phenyl carbinyl acetate, laevo-
menthyl acetate, menthone, iso-menthone, myrcene, myrcenyl acetate,
20 myrcenol, nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alpha-
pinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol,
terpinyl acetate, vertenex (para-tertiary-butyl cyclohexyl acetate), amyl
cinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene,
cinnamic alcohol, couramin, dimethyl benzyl carbinyl acetate, ethyl vanillin,
25 eugenol, iso-eugenol, flor acetate, heliotrophine, 3-cis-hexenyl salicylate,
hexyl salicylate, lilial (para-tertiarybutyl-alpha-methyl hydrocinnamic
aldehyde), gamma-methyl ionone, nerolidol, patchouli alcohol, phenyl
hexanol, beta-selinene, trichloromethyl phenyl carbinyl acetate, triethyl
citrate, vanillin, veratraldehyde, alpha-cedrene, beta-cedrene,
30 C1 5H24sesquiterpenes, benzophenone, benzyl saiicylate, ethylene
brassylate, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8,-hexamethyl-
cyclo-penta-gamma-2-benzopyran), hexyl cinnamic aldehyde, Iyral (4-(4-
hydroxy-4-methyl pentyl)-3-cyclohexene-1 0-carboxaldehyde), methyl
cedrylone, methyl dihydro jasmonate, methyl-beta-naphthyl ketone, musk
35 ambrette, musk idanone, musk ketone, musk tibetine, musk xylol, aurantiol
and phenylethyl phenyl acetate and mixtures thereof.
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W O 97136978 21 PCT~US97/04959
The compositions according to the present invention are suitable for use
where acidic products and surfactants, preferably a cationic surfactant are
present. Such acidic products include fabric softeners, hard surface
cleaners, bathroom cleaners, shower gels, deodorants, bars, shampoos,
conditioners .
Fabric softener comPositions
When used as a fabric softener composition, the cationic surfactants which
also act as fabric softener will preferably be present, depending on the
composition execution, in amount of 1% to 8% by weight where the
composition is in diluted form or in amount of 8% to 80%, more preferably
10% to 50%, most preferably 15% to 35% by weight where the
composition is in concer,lrated form.
The fabric softener composition may also optionally comprise conventional
softening ingredients such as nonionic extenders, surfactants concentration
aids, electrolyte concentration aids, stabilisers, such as well known
antioxidants and reductive agents, Soil Release Polymers, emulsifiers,
bacteriocides, colorants, perfumes, preservatives, optical brighteners, anti
ionisation agents, antifoam agents and enzymes.
Process
Also provided herein by the present invention is a process for preparing a
composition as described herein before, which comprises the steps of
a) mixing the surfactant and optional components, if any, at a temperature
above the melting point of the surfactant,
b) preparing a waterseat,
c) dispersing the mixture prepared in step a) in the waterseat,
d) adding the betaine ester to
d1 )-the mixture prepared under point a), or
d2)- the waterseat under point b), or
d3)-the surfactant dispersion under c), or
d4) combination of any of the above,
e) optionally, cooling the resulting dispersion.
,
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Preferably the molten mixture of step a) will be dispersed in a waterseat of
step b) above the Krafft temperature of the surfactant.
5 The waterseat may optionally contain additives such as polyethylene glycol
or biocide.
Acids may be added in step a) or directly to the waterseat of step b).
Optional components such as dyes, perfumes if present will be added either
before step e) once the resulting dispersion is made or after step e).
Preferably, during dispersion of the betaine ester in step d3), care should be
taken that the temperature of the molten mixture is above the Krafft
temperature of the surfactant. By Krafft temperature is meant the
temperature at which the solubility of the surfactant becomes equal to the
15 critical micelle concentration (CMC), the CMC being defined in M.J ROSEN,
Surfactants and interfacial phenomena, 1 988, p.21 5.
It is also preferred to apply sufficient shear to ensure adequate incorporation
of the betaine ester into the micelles/vesicles. The amount of shear should
20 be sufficient to properly disperse the surfactant. Proper dispersion can be
verified by controlling the particle size of the resulting dispersion, by e.g
microscopy or light scattering techniques. The particle size should
preferably be below 50~m.
25 With regard to the cooling step, it is preferred for optimal storage results to
cool the resulting mixture below the Krafft temperature of the surfactant
before the product is stored.
Not to be bound by theory, it is believed that such a process provides
30 effective protection of the weak ester linkage of the betaine ester by
shielding it from water; thus avoiding premature hydrolysis during storage.
Preferably, for optimum protection provided by this process, the surfactant
used is a cationic surfactant.
35 Perfume synthesis exam~les
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WO 97t36978 23 PCT/US97/04959
1-Svnthesis of N,N-dioctYlqlvcine esters and N,N-didodecvlqlYcine esters of
unhindered alcohols by transesterification
To a mixture of N,N-dioctylglycine methyl ester (47.02 9, 150 mmol, 1 eq)
in toluene (250 ml) under argon was slowly added some sodium methoxide
(1.019, 0.019 mol, 0.125 eq) and geraniol (27.3 ml, 158 mmol, 1.05 eq).
The mixture was heated under vacuum (10 mm Hg) and the methanol
produced by the transesterification reaction is distilled with toluene over one
hour after which the reaction appeared completed by 1 H NMR. Any
remaining toluene is evaporated under vacuum. Diethyl ether was added
(200 ml) and the mixture stored at 4~C for one hour prior to filtration. The
filtrate was then concentrated under vacuum yielding to the expected N,N-
dioctylglycine geranyl ester as a light yellow oil (quantitative yield).
This type of synthesis can also be conveniently applied to the synthesis of
N,N-dioctylglycine phenoxanyl ester; N,N-dioctylglycine cis-3-hexenyl ester
as well as for N,N-didodecylglycine phenoxanyl ester, N,N-didodecylglycine
cis-3-hexenyl ester and N, N-didodecylglycine geranyl ester with the
exception that for the three last one N,N-dioctylglycine methyl ester is used
in the synthesis instead of N,N-dioctylglycine methyl ester.
2-Svnthesis of N,N-dioctvlqlvcine esters and N,N-didodecvlglYcine esters of
hindered alcohols (tertiarv alcohols) using their chloroacetate or
bromoacetate
Dihydromyrcenyl bromoacetate (27.7 9, 100 mmol, 1 eq), in ethyl acetate
(50 ml), was slowly added to dioctylamine (33 ml, 110 mmol, 1.1 eq) and
sodium carbonate ~21.29, 0.2 mol, 2 eq), in ethyl acetate (100 ml). The
reaction mixture was stirred at ambient temperature for 72 hours after
which the reaction seemed completed by 1H NMR. The sodium carbonate
was filtered off, the filtrate was concentrated under vacuum and diethyl
ether (200 ml) was added before storage of the solution at 4~C for 12
hours. Then, the solution was filtered and removal of ether under vacuum
yielded to the expected N,N-dioctylglycine dihydromyrcenyl ester as a
yellow oil (38.059, 87% yield).
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W O 97/36978 24 PCT~US97/04959
Linalyl chloroacetate ~5.77 9, 25 mmol, 1 eq), in toluene (50 ml), was
slowly added to didodecylamine ~10 9, 28.3 mmol, 1.13 eq) and sodium
carbonate (5.3 9, 0.05 mol, 2 eq), in toluene (50 ml). The reaction mixture
5 was stirred at 60~C for two weeks after which the reaction seemed
completed by 1 H NMR. The sodium carbonate was filtered off, the filtrate
was concentrated under vacuum and diethyl ether (200 ml) was added
before storage of the solution at 4~C for 12 hours. Then, the solution was
filtered and removal of ether under vacuum yielded to the expected N,N-
10 didodecylglycine linalyl ester as a yellow oil.
This type of synthesis can also be conveniently applied to the synthesis ofN,N-dioctylglycine esters and N,N-didodecylglycine esters of unhindered
alcohols.
In all these experiments, the N,N-dioctylglycine esters hydrochloride or
hydrobromide and the N, N-didodecylglycine esters hydrochloride or
hydrobromide can be easily obtained by dissolving N,N-dioctylglycine esters
or N,N-didodecylglycine esters in an organic solvant such as methanol,
ethanol, isopropanol, petroleum ether, diethyl ether, toluene and adding at
least a stoechiometric amount of mineral acid in water or in an organic
solvant (such as HCI in isopropanol).
3-Svnthesis of N-dodecvl-N-(2-qeranvloxv-2-oxoethYl)glvcine geranYI ester
bv l-ansesterification (alcohol unhindered)
To a mixture of N-dodecyl-N-(2-methoxy-2-oxoethyl)glycine methyl ester
(6.59 9, 20 mmol, 1 eq) in toluene (80 ml) under argon was slowly added
some sodium methoxide (0.27 9, 0.005 mol, 2*0.125 eq) and geraniol (7.3
ml, 42 mmol, 2*1.05 eq). The mixture was heated under vacuum (10 mm
Hg) and the methanol produced by the transesterification reaction was
distilled with toluene over two hours after which the reaction appeared
completed by 1 H NMR. Any remaining toluene was evaporated under
vacuum. Diethyl ether was added (200 ml) and the mixture stored at 4~C
CA 022~0837 1998-10-01
WO 97136978 PCT/US97/04959
for one hour prior to filtration. The filtrate was then concentrated under
vacuum yielding to the expected N-dodecyl-N-(2-geranyloxy-2-
oxoethyl)glycine geranyl ester as a light brown oil (quantitative yield).
5 This type of synthesis can also be conveniently applied to the synthesis of
N-dodecyl-N-(2-phenoxanyloxy-2-oxoethyl)glycine phenoxanyl ester and N-
dodecyl-N-(2-cis-3-hexenyloxy-2-oxoethyl)glycine cis-3-hexenyi ester as well
as for the synthesis of N-butyl-N-(2-geranyloxy-2-oxoethyl)glycine geranyl
ester, N-butyl-N-(2-phenoxanyloxy-2-oxoethyl)glycine phenoxanyl ester and
10 N-butyl-N-(2-cis-3-hexenyloxy-2-oxoethyl)glycine cis-3-hexenyl ester with
the exception that for the three last one N-butyl-N-(2-methoxy-2-
oxoethyl)glycine methyl ester is used in the synthesis instead of N-dodecyl-
N-(2-methoxy-2-oxoethyl)glycine methyl ester.
15 4-Svnthesis of N-dodecvl-N-(2-linalvloxv-2-oxoethvl~glvcine linalYI ester or
N-dodecvl-N-(2-dihvdromvrcenyloxv-2-oxoethvl~glycine dihydromvrcenvl
ester (stericallv hindered alcohol such as tertairY alcohols) using their
chloroacetate or bromoacetate
Dihydromyrcenyl bromoacetate (55.44 9, 200 mmol, 2 eq), in acetonitrile
(75 ml), was slowly added to dodecylamine (24.2 ml, 100 mmol, 1 eq) and
sodium carbonate (42.4 g, 0.4 mol, 4 eq), in acetonitrile (250 ml). The
reaction mixture was stirred at ambient temperature for 48 hours after
which the reaction seemed completed by 1H NMR. The sodium carbonate
was filtered off, the filtrate was concentrated under vacuum and diethyl
ether (200 ml) was added before storage of the solution at 4~C for 12
hours. Then, the solution was filtered and removal of ether under vacuum
yielded to the expected N-dodecyl-N-(2-dihydromyrcenyloxy-2-
oxoethyl)glycine dihydromyrcenyl ester as a brown oil (56.2 9, 97.2%
yield).
Linalyl chloroacetate (55.04 9, 200 mmol, 2 eq), in acetonitrile (75 ml),
was slowly added to dodecylamine (24.2 ml, 100 mmol, 1 eq) and sodium
carbonate (42.4 9, 0.4 mol, 4eq), in acetonitrile (50 ml). The reaction
mixture was stirred at 50~C for two weeks after which the reaction seemed
completed by 1 H NMR. The sodium carbonate was filtered off, the filtrate
was concentrated under vacuum and diethyl ether (200 ml) was added
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WO 97/36978 26 PCT/US97/04959
before storage of the solution at 4~C for 12 hours. Then, the solution was
filtered and removal of ether under vacuum yielded to the expected N-
dodecyl-N-(2-linalyloxy-2-oxoethyl)glycine linalyl ester as a brown oil (48.6
9, 84.7% yield).
Synthesis of N-butyl-N-(2-linalyloxy-2-oxoethyl)glycine linalyl ester and N-
butyl-N-(2-dihydromyrcenyloxy-2-oxoethyl)glycine dihydromyrcenyl ester is
made as above with the exception that butylamine is used in the synthesis
instead of dodecylamine
This type of synthesis can also be conveniently applied to the chloroacetate
or bromoacetate of unhindered alcohols such as geraniol, phenoxanol, cis-3-
hexenol.
15 In all these experiments, the hydrochloride or hydrobromide salts can be
obtained by dissolving for example N-butyl-N-(2-geranyloxy-2-
oxoethyl)glycine geranyl ester in an organic solvant such as methanol,
ethanol, isopropanol, petroleum ether, diethyl ether, toluene and adding at
least a stoechiometric amount of mineral acid (HCI or HBr) in water or an
20 organic solvant (such as HCI in isopropanol).
5-Svnthesis of N.N-bis(2-geranvloxy-2-oxoethvl)qlvcine geranvl ester bv
transesterification ~or anv unhindered alcohol)
To a mixture of N,N-bis(2-methoxy-2-oxoethyl)glycine methyl ester (7.0 9,
30 mmol, 1 eq) in toluene (80 ml) under argon was slowly added some
sodium methoxide (0.49 9, 0.009 mol, 3*0.10 eq) and geraniol (14.57 9,
95 mmol, 3*1.05 eq). The mixture was heated under vacuum (10 mm Hg)
and the methanol produced by the lla,.seslerification reaction is distilled
with toluene over two hours after which the reaction appeared completed
by 1H NMR. Any remaining toluene is evaporated under vacuum. Diethyl
ether was added (200 ml) and the mixture stored at 4~C for one hour prior
to filtration. The filtrate was then concentrated under vacuum yielding to
the expected N,N-bis(2-geranyloxy-2-oxoethyl)glycine geranyl ester as a
yellow oil (quantitative yield).
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WO 97/36978 27 PCT/US97/04959
This type of synthesis can also be conveniently applied to the synthesis of
N,N-bis(2-phenoxanyloxy-2-oxoethyl)glycine phenoxanyl ester and N,N-
bis(2-cis-3-hexenyloxy-2-oxoethyl)glycine cis-3-hexenyl ester.
5 ~-Synthesis of N,N-bis(2-linalyloxv-2-oxoethvl)glvcine linalYI ester or N,N-
bis(2-dihYdromyrcenYloxY-2-oxoethYl)glycine dihydromvrcenyl ester
(stericallv hindered alcohols such as tertairv alcohols) using their
chloroacetate or bromoacetate
Dihydromyrcenyl bromoacetate (83.16 9, 300 mmol, 3 eq), in acetonitrile
(100 ml), was slowly added to ammonia (50 ml of 2N solution in 2-
propanol, 100 mmol, 1 eq) and sodium carbonate (63.6 9, 0.6 mol, 6 eq),
in acetonitrile (350 ml). The reaction mixture was sealed and stirred at
ambient temperature for 48 hours after which the reaction seemed
completed by 1 H NMR. The sodium carbonate was filtered off, the filtrate
was concentrated under vacuum and diethyl ether (200 ml) was added
before storage of the solution at 4~C for 12 hours. Then, the solution was
filtered and removal of ether under vacuum yielded to the expected N,N-
bis(2-dihydromyrcenyloxy-2-oxoethyl)glycine dihydromyrcenyl ester as a
brown oil.
Linalyl chloroacetate (82.56 9, 300 mmol, 3 eq), in acetonitrile (100 ml),
was slowly added to ammonia (50 ml of 2N solution in 2-propanol, 100
mmol, 1 eq) and sodium carbonate (63.6 9, 0.6 mol, 6 eq), in acetonitrile
(350 ml). The reaction mixture was stirred at 50~C for two weeks after
which the reaction seemed completed by 1H NMR. The sodium carbonate
was filtered off, the filtrate was concerlraled under vacuum and diethyl
ether (200 ml) was added before storage of the solution at 4~C for 12
hours. Then, the solution was filtered and removal of ether under vacuum
yielded to the expected N,N-bis(2-linalyloxy-2-oxoethyl)glycine linalyl ester
as a brown oil.
This type of synthesis can also be conveniently applied to the synthesis of
chloroacetate or bromoacetate of unhindered alcohols such as geraniol,
phenoxanol, cis-3-hexenol.
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WO 97/36978 28 PCT/US97/04959
In all these experiments, the hydrochloride or hydrobromide salts can be
obtained by dissolving for example N,N-bis~2-linalyloxy-2-oxoethyl)glycine
linalyl ester in an organic solvant such as methanol, ethanol, isopropanol,
petroleum ether, diethyl ether, toluene and adding at least a stoechiometric
5 amount of mineral acid (HCI or HBr) in water or an organic solvant (such as
HCI in isopropanol).
The invention is illustrated in the following non-limiting examples, in which
all percentages are on a weight basis unless otherwise stated.'
In the examples, the abbreviated component identifications have the
following meaning:
DEQA : Di-(tallowoyl-oxy-ethyl) dimethyl ammonium chloride
Fatty acid : Stearic acid of IV= 1
Electrolyte : Calcium chloride
DGGE : N-dodecylglycine geranyl ester hydrochloride
PEG : Polyethylene Glycol 4000
CTAB : C 16 trimethyl ammonium bromide
Celrin)ide : C14 trimethyl ammonium bromide
Dobanol~ 23-3 : C12-C13 ethoxylated alcohol with an average degree of
ethoxylation of 3, available from Shell
Lutensol~ A0 30 : C13-15 alcohol ethoxylated with an average degree of
ethoxylation of 30, available from BASF
Dobanol~91-10 : C19-C21 ethoxylated alcohol with an average degree of
ethoxylation of 10, available from Shell
Dobanol~9 23-6.5 : C12-C13 ethoxylated alcohol with an average degree of
ethoxylation of 6.5, available from Shell
Alkyl sulphate : Based on Isalchem 123 ~ alcohol, C12-13 alcohol, 94%
branched, available from Enichem
ExamPle 1
-
The following fabric softening compositions according to the present
20 invention were prepared:
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W O 97136978 PCTNS97/04959
Component A B C D E
DEQA 2.6 2.9 18.0 19.0 19.0
Fatty acid 0.3 - 1.0
Hydrochloride acid 0.02 0.02 0.02 0.02 0.02
PEG - - 0.6 0.6 0.6
Perfume 1.0 1.0 1.0 1.0 1.0
Silicone antifoam 0.01 0.01 0.01 0.01 0.01
DGGE 1 0.5 1 0.5
Electrolyte - - 600ppm 600ppm 1200ppm
Dye 1 Oppm 1 Oppm 50ppm 50ppm 50ppm
Water and minors to balance to 100
ExamDle 2
5 The following hard surface cleaner compositions according to the present
invention were prepared by mixing the listed ingredients
F G H
CTAB 3.2
Cetrimide - 4.2
C8-10 dimethyl - - - 4.40
amine oxide
Lutensol(~) AO 30 - - 0.75 3.0
Dobanol~ 91 - 10 - - 2.60
Dobanol~ 23-6.5 - - O.9O
Dobanol~ 23-3 - - 1.75
Maleic acid 8.0 8.6
Citric acid - - - 5.50
Alkyl sulphate - - - 4.0
Ammonia (as - - - 0.40
NH40H~
Propane diol - - - 1. 30
H?07 - - 7 0
H7S04 up to pH - - 4.0
DGGE 1.0 0.5 1.0 0.6
CA 02250837 1998-10-01
W O 97/36978 30 PCTrUS97/04959
water and miscellaneous to balance
pH as is ¦ 1.0 ¦ 0.9 ¦ 4.0 ¦ 3.2
