Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2001-07-31
2002-07-30
Kumar, Shailendra (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S134000, C564S142000, C564S154000, C514S618000, C514S619000, C514S620000, C424S059000, C424S401000, C424S701000, C424S709000
Reexamination Certificate
active
06426435
ABSTRACT:
FIELD OF INVENTION
The invention relates to substantive water-soluble his-quatemary salts of cinnamidoalkylamines. More particularly, the invention relates to novel, cationic, non-hydrolysable, non-irritating UV-absorbing bis-quaternary salts of cinnamidoalkylamines which are substantive to fabric, skin and hair. The invention also relates to a process of manufacture of the said compounds and further to their use in hair, skin and fabric care formulations.
BACKGROUND AND PRIOR ART
The harmful effects of solar UV-radiation on skin are well known. The UV-B (290-320 nm) portion of solar spectrum is largely responsible for erythema (sunburn) and cancer. [M. M. Rieger, Cosmet. Toiletries, 102 (3), 91, (1987); L. Taylor, Skin Cancer Foundation J., 4, (90) (1986)].
Similarly, photodegradative effect of UV-radiation on human hair is well documented. Continuous exposure to sunrays makes human hair color and makes human hair rough, brittle and difficult to comb. UV rays are reported to damage the proteins of cuticles. Prolonged irradiation results in diminished tensile strength due to breaking of disulphide bonds in keratin, [R. Beyak et al, J. Soc. Cosmet. Chem. 22, 667-668 (1971), E. Hoting et al, J. Soc. Cosmet. Chem. 46, 85-99 (1995)].
In addition, UV light is also known to fade garments. [P. C. Screws, Text. Chem. Color, 11, 21 (1987); B. Milligan et al, Polym. Degrad. Stab. 10 (4), 335 (1985)].
A number of UV-absorbing compounds like derivatives of salicylic acid, benzophenones, benzotriazoles, cinnamic acid have been used in personal care products. However, all these molecules suffered from a major disadvantage of lack of substantivity. To make this UV-absorbing moieties more substantive, structural modification have been introduced.
U.S. Pat. No. 5,601,811 (1997) describes substantive UV-absorbing quaternary ammonium compounds containing cinnamidoalkylamine and product compositions for detergents, household cleaners and hair and skin personal care products. However, these products are said to be either water-soluble or water-dispersible. Bis-quaternary compounds of U.S. Pat. No. 4,734,277 (1988) are synthesised from cinnamidoalkylamine and alkylchlorohydrin forming a linker of an alkyl group with a hydroxyl group beta to one of the quaternary nitrogens, thus giving an unsymmetrical bis-quaternary molecule.
The main object of the present invention is therefore to synthesise highly water-soluble molecules containing cinnamido moiety to provide UV absorption and with cationic centre to provide substantivity to skin, hair and fabric.
The inventors have found that symmetrical bifunctional quaternising agents with oxyethylene linkage in the synthesis of UV-absorbing bis-quaterneries boosts hydrophilicity. High water solubility is desirable because these kind of substantive compounds can be formulated in oil-free compositions so that greasy feel of cosmetic preparations based on hydrophobic carrier can be avoided. Due to their substantive nature constant reapplication of the sunscreen preparation is not necessary in activity like swimming. Hence, the compounds of the present invention are designed to address the need for highly water-soluble yet substantially substantive sunscreen molecules.
SUMMARY OF THE INVENTION
Thus the present invention provides novel, substantive, water-soluble bis-cinnamidoalkylamine quaternary compounds of Formula I,
wherein R
1
represents up to four substituents, same or different, selected from H, halo, —OH, —NH
2
, —NO
2
, —OCH
3
, —N(CH
3
)
2
, alkyl groups containing up to 6 carbon atoms, alkoxy groups containing up to 6 carbon atoms, alkylamino or N,N-dialkylamino groups containing up to 6 carbon atoms;
R
2
is selected from hydrogen, alkyl group containing up to 6 carbon atoms;
R
3
and R
4
are independently selected from benzyl, alkyl group containing up to 6 carbon atoms;
n is an integer from 1 to 6; rn is an integer from 1 to 10;
X
−
is a counter anion of quaternary centres selected from halides including chloride, bromide, iodide and methane sulphonate and its derivatives such as trifluoro methane sulphonate, benzene sulphonates including its p-bromo, nitro and methyl derivatives.
The invention further relates to a process of making a water-soluble quaternary ammonium salt of bis-cinnamidoalkylamine of Formula I
wherein R
1
represents up to four substituents, same or different, selected from H, halo, —OH, —NH
2
, —NO
2
, —OCH
3
, —N(CH
3
)
2
, alkyl groups containing up to 6 carbon atoms, alkoxy groups containing up to 6 carbon atoms, alkylamino or N,N-dialkylamino groups containing up to 6 carbon atoms;
R
2
is selected from hydrogen, alkyl group containing up to 6 carbon atoms;
R
3
and R
4
are independently selected from benzyl, alkyl group containing up to 6 carbon atoms;
n is an integer from 1 to 6; m is an integer from 1 to 10;
—X
−
is a counter anion of quaternary centres selected from halides including chloride, bromide, iodide and methane sulphonate and its derivatives such as trifluoro methane sulphonate, benzene sulphonates including its p-bromo, nitro and methyl derivative;
wherein, a compound of Formula II is first reacted with a compound of Formula III and the intermediate of Formula IV thus obtained is quatemised with a compound of Formula V,
wherein in all these Formulae, R
1
, R
2
, R
3
, R
4
, m, n and X
−
have the same meaning as Formula I and R
5
of Formula II is selected form —OH, Cl
−
or —O(CH
2
)
p
CH
3
with p=0 to 3.
In another aspect this invention provides compositions containing quaternary ammonium compounds that are water-soluble, UV-absorbing and substantive to skin, hair and textile fibres. The unique combination of substantivity to hair and skin, strong UV absorption and water-solubility of these quaternary compounds of bis-cinnamidoalkylamines is very desirable for personal care products, especially for skin care applications.
DETAILED DESCRIPTION OF THE INVENTION
The UV absorbing compounds of the present invention are quaternary salts of cinnamidoalkylamines that are prepared by reacting lower alkyl ester of cinnamic acid or acid halides of cinnamic acid with an amino compound that is subsequently quaternised with bifunctional alkylating agents.
In the process, the amidification reaction between a compound of the Formula II when R
5
=—OH or —O(CH
2
)
p
CH
3
(p=0 to 3), with that of Formula Ill is carried out at from about 120° C. to about 200° C., under pressure from about 10 psi to about 100 psi, in the presence of a basic catalyst such as sodium methoxide, sodium hydroxide from 0.25% to 5.0% by weight of the reaction mass, to afford the intermediate compound of Formula IV.
Preferred amount of such catalyst is 1.0% w/w of total reaction mass. The reaction is conveniently monitored by TLC or HPLC using UV detection. After the complete disappearance of cinnamic acid ester, the excess diamine is distilled off under vacuum.
Alternately, this reaction is carried out in the presence of a basic catalyst such as sodium methoxide, sodium hydroxide from 0.25% to 5.0% by weight of the reaction mass under atmospheric pressure, under blanket of nitrogen, with an arrangement for continuous selective removal of lower alcohol formed in the reaction.
Thus, the condensation reaction of one mole of cinnamic acid ester is carried with 1.0 to 3.0 moles of diamine at 120 to 200° C., preferably at 180° C., for 12 to 36 hours. The amines themselves can catalyse the reaction, however, the rates are found to be slower as compared with the bases like sodium methoxide and the like.
The same reaction can be performed using cinnamic acid in place of cinnamic acid ester at temperatures up to 200° C. and pressures of 100 psi, keeping the same stoichiometry (1:1.0 to 3). The excess diamine serves as solvent for the reaction.
Cinnamic acid esters and amino compounds are selected that are liquid within the disclosed temperature and pressure range.
The amidification reaction between a compound of Formula II when R
5
=—Cl in the presence of a solvent, is c
Jadhav Tanaji Shamrao
Jawale Arun Harchandra
Koshti Nirmal Madhukar
Moghe Manasi Dattatraya
Naik Shubhangi Dattaram
Birch & Stewart Kolasch & Birch, LLP
Galaxy Surfactants Ltd.
Kumar Shailendra
LandOfFree
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