CA1157879A - Derivatives of 2-oxazolines useful as intermediates in the preparation of antioxidants - Google Patents
Derivatives of 2-oxazolines useful as intermediates in the preparation of antioxidantsInfo
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- CA1157879A CA1157879A CA000332528A CA332528A CA1157879A CA 1157879 A CA1157879 A CA 1157879A CA 000332528 A CA000332528 A CA 000332528A CA 332528 A CA332528 A CA 332528A CA 1157879 A CA1157879 A CA 1157879A
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- Prior art keywords
- butyl
- hydroxyphenyl
- amino
- propionate
- alkyl
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Novel derivative of 2-oxazolines are useful as inter-mediates in the preparation of antioxidants which in turn are useful in protecting organic materials such as synthetic and natural rub-bers, petroleum products, and plastics from oxidative degradation.
The present invention relates to compounds of the formula:
(3-R-5-R1-9-C6H2OH)CH2CH2COOCH2C(B)(D)-K
wherein R and R1 may be the same or different and are C1-C12 alkyl; B and D may be the same or different and are hydrogen, C1-C4 alkyl, -CH2OH or -CH2OOCZ wherein Z is hydrogen, C1-C17 alkyl, phenyl or -CH2CH2(3-R-5-R1-4-C6N2OH) wherein R and R1 have the meanings above; and K is -NH2 or -NH2 HL wherein L
is a halogen anion.
Novel derivative of 2-oxazolines are useful as inter-mediates in the preparation of antioxidants which in turn are useful in protecting organic materials such as synthetic and natural rub-bers, petroleum products, and plastics from oxidative degradation.
The present invention relates to compounds of the formula:
(3-R-5-R1-9-C6H2OH)CH2CH2COOCH2C(B)(D)-K
wherein R and R1 may be the same or different and are C1-C12 alkyl; B and D may be the same or different and are hydrogen, C1-C4 alkyl, -CH2OH or -CH2OOCZ wherein Z is hydrogen, C1-C17 alkyl, phenyl or -CH2CH2(3-R-5-R1-4-C6N2OH) wherein R and R1 have the meanings above; and K is -NH2 or -NH2 HL wherein L
is a halogen anion.
Description
IN THE PREPARATTON O~ ANTIOXIDANTS
_ BACKGROUND OF THE INVENTION
The present invention relates to derivatives o:~ 2-oxazo-lines useful as in-termediates in the preparation of antioxidants.
Such antioxidan-ts are disclosed in U.S. Pa-tent No. 4,145,556 issued March 20, 1979.
SUMM~RY OF THE INVE:NTION
The presen-t invention relates to compounds of -the formula l 11 . I
W_ n D
where in K is NH2 or -NH2. HL and L is a halide anion :Eor ex-ample, chloride, bromide or iodide, wherein B is hydros~en, Cl to C4 alkyl, -CH2OH or -CH2OC-Y; Y is hydrogen, C1 -to C30 alkyl, C4 to C8 cycloalkyl, C6 to C10 aryl, substituted aryl or A, wherein A is R~
H0 .~ ~ CH2-CH2-, II
R~
-wherein R and R1 may be the same or different and are C1 to C12 alkyl or C8 -to C10 aralkyl; D is hydrogen, Cl -to C4 al~l, -CH2OH
o or CH2OC-Z, wherein Z is hydrogen, C1 to C30 alkyl, C4 to C8 cycloalkyl~ C6 to C10 aryl~ C6 to C10 substituted aryl, A, wherein .~
_ BACKGROUND OF THE INVENTION
The present invention relates to derivatives o:~ 2-oxazo-lines useful as in-termediates in the preparation of antioxidants.
Such antioxidan-ts are disclosed in U.S. Pa-tent No. 4,145,556 issued March 20, 1979.
SUMM~RY OF THE INVE:NTION
The presen-t invention relates to compounds of -the formula l 11 . I
W_ n D
where in K is NH2 or -NH2. HL and L is a halide anion :Eor ex-ample, chloride, bromide or iodide, wherein B is hydros~en, Cl to C4 alkyl, -CH2OH or -CH2OC-Y; Y is hydrogen, C1 -to C30 alkyl, C4 to C8 cycloalkyl, C6 to C10 aryl, substituted aryl or A, wherein A is R~
H0 .~ ~ CH2-CH2-, II
R~
-wherein R and R1 may be the same or different and are C1 to C12 alkyl or C8 -to C10 aralkyl; D is hydrogen, Cl -to C4 al~l, -CH2OH
o or CH2OC-Z, wherein Z is hydrogen, C1 to C30 alkyl, C4 to C8 cycloalkyl~ C6 to C10 aryl~ C6 to C10 substituted aryl, A, wherein .~
-2~ 7B1;~3 A is as de:fined above, or Z is a divalent group connecting -two esteramine moieties; n is an inteyer equal to O or 1; with the pro-viso -tha t when n is 0, X is hydrogen, Cl to C30 alkyl, C~ to C8 cycloalkyl, C6 to C10 aryl, subs titu ted aryl, A, wherein A is as defined above, or O B
Il I
-Q-C-o-CH2--C ~K
wherein Q is C~ to C8 alkylene, thiodie thylene or phenylene, with the proviso that Q and Z cannot bo-th be divalent at the same -time and -tha-t either X must be the radical A, or if X is not -the radical o A, then B must be the radical E, wherein E is -CH2-0-C-A, and when n is 1, W is -CH20H or E, wherein E is defined above, V is C1 to Ca~ alkyl, -CH20H or E, wherein E is as defined above, X is C1 to C30 alkyl, C~ to C8 cycloalkyl, C6 to C~O aryl, substitu ted aryl, the radicals R W o s HO --~,~ CH2 or -Q--V --COCH2C--K
wherein R and R1 are defined above, Q is C2 to C6 alkylene, thiodimethylene or phenylene, with the provisio that Q and Z cannot be divalent at the same time and that either X must be a radical of the formula II or B or W mus-t be E, wherein E is as defined above.
The terms alkyl and alkylene comprise linear and branched moieties and the term cycloalkyl includes bridged and non-bridged groups.
~, Y!
The compounds of the present inven-tion are use~ul as intermediates for -the preparation of antioxidants for protecting organic materials that are normally subject -to oxidative de0rada-tion.
Examples of such antioxidants are disclosed in U . S .
Patent No. 4,145,556 -to Hirsch et al, issued March 20, 1979. An intermecliate compound of this invention may be used to prepare (N, Nl-bis [2- (3, 5-di--t-butyl -4-hydroxyphenyl)propionyloxye-thyl) oxamide (hereinafter called "BPEO") which is an an-tioxidan-t dis-closed in the above mentioned Hirsch e-t al patent (example 1). The antioxidant properties of BPEO and the o-ther antioxidants disclosed in the Hirsch et al patent are set forth at column 5 lines 16-59 and Examples IX-XIV of said pa-tent.
The process by which these compounds of the invention may be converted into antioxidants includes, for example in -the case of BPEO, condensing (3, 5-di--t-C4Hg-4-C6H2OH)CH2CH2 COOCH2 CH2NH2 with oxalic acid or acid chloride using well known amidation conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the compounds of the present invention E~ and R1 are preferably C~ to C12 alkyl and are mos-t preferably tertiary butyl.
Aryl or phenyl groups of the compounds of the present invention are preferably substituted with one or more hydroxy, halogen (e.g.
fluorine, chlorine, bromine or iodine), C1 to C12 alkyl, amino, or nitro groups. The substituents on the aryl group may be the same or different. Preferred divalent groups connecting two esteramine moieties are ca:rbon-carbon bonds, C1 to C8 alkylene, thiodiethylene and phenylene.
The ammonium sal-ts of the presen-t invention may be prepared by hydrolysis of oxazoline of the Formula II
, . ~ . ~ . .
.
-3a-7~ ~3 o _ V / I I I
N--D
wherein ~, V, W, B, D, and n are defined as above.
The amines of Formula I wherein K is -NH2, of the pre-sent inven-tion are prepared by neu-traliza-tion of the ammonium salts of Formula I wherein K is -N~12. HL and L is as defined above.
The hydrolysis is carried ou-t by reac-ting the oxazoline of formula III with a stoichiometric amount of a mineral acid and a stoichiome-tric amount of wa-ter in the presence of a sui-table solvent.
The neutralization is carried out by adding an aqueous solution of a base to a cool solution of the amine hydrohalide of that formula I until the solution is slightly basic.
Exan~ples of suitable acids that may be used in this hy-drolysis are hydrochloric, hydrobromic, hydroiodic, phosphoric, nitiric and sulfuric.
Examples of sui table slovents that may be used in this invention are diethylether, methylene chloride, dichloroethane, chlorobenzene, chloroform, hexane, petroleum either, benzene, toluene, xylene, di-n-propylether, di-n-bu-tyle ther, diphenylether, tetrahydrofuran, me-thanol, ehtanol, n-propanol, isopropanol, n-butanol, -t-butanol, cyclohexanol, hexanol, dimethyl formamide and dimethylsulfoxide .
Examples of the suitable bases that may be used in the execution of this invention are ammonium hydroxide, li-thium hy-droxide, magnesium hydroxide, sodium bicarbonate, sodium car-bonate, potassium carbonate and potassium bicarbonate.
The foregoing list of mineral acids, bases and solvents is representative of materials used in the execution of the invention and is by no means exhaustive.
~....
~'713 ~
The followin~ list of compounds is representative of compounds of the present inventi.on and is by no means ex-haustive.
2-Aminopropyl 3-13,5-di-t-butyl-4-hydroxyphenyl)~
propionate 2-Aminopropyl 3-(3,5-di-t:-butyl-4-hydroxyphenyl~-propionate hydrochloride 2-Amino-3-methylpentyl[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]
2-Amino-3-methylpentyl[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]hydrobromide 2-Amino-2-methylpropyl[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]
2-Amino-2-methylpropyl[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]hydroiodide 2-Amino-2-(hydroxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(acetoxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino(acetoxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate~hydrochloride 2-Amino-2-(hexanoyloxymethyl)propyl[3-(3,5~di-t butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(dodecanoyloxymethyl)propyl[3~(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(stearoyloxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(benzoxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-methyltrimethylene bis~3-(3,5-di-t-butyl-4-hy~roxyphenyl)propionate]
,;
2-Amino-2-(hydroxymethyl~butyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(Acetoxy methy:l.)butyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(hexanoyloxy methyl)butyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(dodecanoyloxy methyl)butyl[3-(3,5-di~t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(stearoyloxy methyl)butyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(benzoxymethyl) butyl[3-(3,5~di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-ethyl trimethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(hydroxymethyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(acetoxy methyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(hexanoyloxy methyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyllpropionate]
2-Amino-2-(dodecanoyloxy methyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate~
2-Amino-2-(stearoyloxy methyl)-3-hydroxypropyl E 3~(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(benzoxy methyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(hydroxymethyl)trimethylene bis[3-~3,5-di-t-butyl-4-hydroxyphenyl)propionate]
~L~L t~
2-Amino-2-(acetoxy)methyltrimethylenebis[3-~3,5-di-t~butyl-4-hydroxyphenyl)propionate]
.2-Amino-2-(hexanoyloxy)methyltrlmethylenebis[3-~3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(dodecanoyloxy)methyltrimethylenebis~3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(stearoyloxy)methyltrimethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(benzoxy)methyltrimethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-isobutanetriyltris[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-isobutanetriyltris[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]hydrochloride 2-Amino-2-[3-(3,5-di-t-butyl-4~hydroxyphenyl)propion-oyloxy]methyltrimethylene diacetate 2-Amino-2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-oyloxy]methyltrimethylene dihexanoate 2-Amino-2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-oyloxy]methyltrimethylene didecanoate 2-Amino-2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-oyloxy]methyltrimethylene distearate 2-Amino-2-13-(3,5-di-t-butyl-~-hydroxyphenyl)propion-oyloxy]methyltrimethylene dibenzoate Example 1 2-Amino-2-methylpropyl[3-(3,5-di-t- utyl-4-hyd oxy-~henyl)propionate].
In a 1 liter, three-neck, round-bottom flask equipped with a thermometer, stirrer and condenser were placed 66.2 g (0.2 moles) 2-[3-~3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-4,4-dimethyl-'7~
2-oxazoline, 400 ml isopropanol and 33 ml 6N hydrochloric acid.
The mixture was heated to 45C for 2 hours and then cooled.
To this stirred solution was added 250 ml of water and 33 ml of 6N sodium hydroxide. The product was removed by filtration and dried. The title compound, thus obtained, melted at 97-99C
Example 2 2-Amino isobutanetriyl tris~3-(3,5-d_-t-butyl-4-_~_roxyphenyl)propionate]
to 44.2g (0.05 moles) of 2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-2-oxazoline-4,4-dimethyl bis~3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] in 200 ml of toluene was added 8.2 ml of 6N hydrochloric acid. After the mixture was stirred for 3 hours, 6 g of sodium carbonate were added. The mixture was stirred for 15 minutes and the layers were separated.
The amine was not isolated; it was used as is in subsequent re-actions.
Example 3 2-Amino-2-ethyltrimethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)pro~ionatelhydrochloride.
In a 2 liter, three-neck, round-bottom flask equipped with a therm~ter, stirrer and condenser were placed 298g (0.48 moles) of 2-[3-(3,5-di-t-butyl-4-hydroxyphenyl~ethyl]-4-ethyl-2-oxazoline-4-methyl[3-(3/5-di-t-butyl-4-hydroxyphenyl)propion-ate], 800 ml of :isopropanol and 90 ml of 6N hydrochloric acid.
The mixture was refluxed for 4 hours. The isopropanol was re-moved and the residue was refluxed in a 2:1 mixture of hexane-toluene to remove the residual water. On cooling the product crystallized. It was removed by filtration and dried. The melting point was 144~150C.
.X
7~f~
Example 4 2-Amino-2-methyltrimethylene b~sE3-~3,s-di-t-butyl-4-hydroxyphenvl)~ropionate]hydrochloride.
The title compound was prepared as described in Ex-ample 3 except that 451 g ~0.743 mo:Les~ of 2-E2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-4-methyl-2-oxazoline-4-methyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] were used instead of 0.48 moles of 2-[2-(3,5-di~t-butyl-4-hydroxyphenyl)ethyl]-4-ethyl-2-oxazoline-4-methyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-ate]. The title compound melted at 161-166C.
,X
Il I
-Q-C-o-CH2--C ~K
wherein Q is C~ to C8 alkylene, thiodie thylene or phenylene, with the proviso that Q and Z cannot bo-th be divalent at the same -time and -tha-t either X must be the radical A, or if X is not -the radical o A, then B must be the radical E, wherein E is -CH2-0-C-A, and when n is 1, W is -CH20H or E, wherein E is defined above, V is C1 to Ca~ alkyl, -CH20H or E, wherein E is as defined above, X is C1 to C30 alkyl, C~ to C8 cycloalkyl, C6 to C~O aryl, substitu ted aryl, the radicals R W o s HO --~,~ CH2 or -Q--V --COCH2C--K
wherein R and R1 are defined above, Q is C2 to C6 alkylene, thiodimethylene or phenylene, with the provisio that Q and Z cannot be divalent at the same time and that either X must be a radical of the formula II or B or W mus-t be E, wherein E is as defined above.
The terms alkyl and alkylene comprise linear and branched moieties and the term cycloalkyl includes bridged and non-bridged groups.
~, Y!
The compounds of the present inven-tion are use~ul as intermediates for -the preparation of antioxidants for protecting organic materials that are normally subject -to oxidative de0rada-tion.
Examples of such antioxidants are disclosed in U . S .
Patent No. 4,145,556 -to Hirsch et al, issued March 20, 1979. An intermecliate compound of this invention may be used to prepare (N, Nl-bis [2- (3, 5-di--t-butyl -4-hydroxyphenyl)propionyloxye-thyl) oxamide (hereinafter called "BPEO") which is an an-tioxidan-t dis-closed in the above mentioned Hirsch e-t al patent (example 1). The antioxidant properties of BPEO and the o-ther antioxidants disclosed in the Hirsch et al patent are set forth at column 5 lines 16-59 and Examples IX-XIV of said pa-tent.
The process by which these compounds of the invention may be converted into antioxidants includes, for example in -the case of BPEO, condensing (3, 5-di--t-C4Hg-4-C6H2OH)CH2CH2 COOCH2 CH2NH2 with oxalic acid or acid chloride using well known amidation conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the compounds of the present invention E~ and R1 are preferably C~ to C12 alkyl and are mos-t preferably tertiary butyl.
Aryl or phenyl groups of the compounds of the present invention are preferably substituted with one or more hydroxy, halogen (e.g.
fluorine, chlorine, bromine or iodine), C1 to C12 alkyl, amino, or nitro groups. The substituents on the aryl group may be the same or different. Preferred divalent groups connecting two esteramine moieties are ca:rbon-carbon bonds, C1 to C8 alkylene, thiodiethylene and phenylene.
The ammonium sal-ts of the presen-t invention may be prepared by hydrolysis of oxazoline of the Formula II
, . ~ . ~ . .
.
-3a-7~ ~3 o _ V / I I I
N--D
wherein ~, V, W, B, D, and n are defined as above.
The amines of Formula I wherein K is -NH2, of the pre-sent inven-tion are prepared by neu-traliza-tion of the ammonium salts of Formula I wherein K is -N~12. HL and L is as defined above.
The hydrolysis is carried ou-t by reac-ting the oxazoline of formula III with a stoichiometric amount of a mineral acid and a stoichiome-tric amount of wa-ter in the presence of a sui-table solvent.
The neutralization is carried out by adding an aqueous solution of a base to a cool solution of the amine hydrohalide of that formula I until the solution is slightly basic.
Exan~ples of suitable acids that may be used in this hy-drolysis are hydrochloric, hydrobromic, hydroiodic, phosphoric, nitiric and sulfuric.
Examples of sui table slovents that may be used in this invention are diethylether, methylene chloride, dichloroethane, chlorobenzene, chloroform, hexane, petroleum either, benzene, toluene, xylene, di-n-propylether, di-n-bu-tyle ther, diphenylether, tetrahydrofuran, me-thanol, ehtanol, n-propanol, isopropanol, n-butanol, -t-butanol, cyclohexanol, hexanol, dimethyl formamide and dimethylsulfoxide .
Examples of the suitable bases that may be used in the execution of this invention are ammonium hydroxide, li-thium hy-droxide, magnesium hydroxide, sodium bicarbonate, sodium car-bonate, potassium carbonate and potassium bicarbonate.
The foregoing list of mineral acids, bases and solvents is representative of materials used in the execution of the invention and is by no means exhaustive.
~....
~'713 ~
The followin~ list of compounds is representative of compounds of the present inventi.on and is by no means ex-haustive.
2-Aminopropyl 3-13,5-di-t-butyl-4-hydroxyphenyl)~
propionate 2-Aminopropyl 3-(3,5-di-t:-butyl-4-hydroxyphenyl~-propionate hydrochloride 2-Amino-3-methylpentyl[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]
2-Amino-3-methylpentyl[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]hydrobromide 2-Amino-2-methylpropyl[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]
2-Amino-2-methylpropyl[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate]hydroiodide 2-Amino-2-(hydroxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(acetoxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino(acetoxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate~hydrochloride 2-Amino-2-(hexanoyloxymethyl)propyl[3-(3,5~di-t butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(dodecanoyloxymethyl)propyl[3~(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(stearoyloxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(benzoxymethyl)propyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-methyltrimethylene bis~3-(3,5-di-t-butyl-4-hy~roxyphenyl)propionate]
,;
2-Amino-2-(hydroxymethyl~butyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(Acetoxy methy:l.)butyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(hexanoyloxy methyl)butyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(dodecanoyloxy methyl)butyl[3-(3,5-di~t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(stearoyloxy methyl)butyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(benzoxymethyl) butyl[3-(3,5~di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-ethyl trimethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(hydroxymethyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(acetoxy methyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(hexanoyloxy methyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyllpropionate]
2-Amino-2-(dodecanoyloxy methyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate~
2-Amino-2-(stearoyloxy methyl)-3-hydroxypropyl E 3~(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(benzoxy methyl)-3-hydroxypropyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(hydroxymethyl)trimethylene bis[3-~3,5-di-t-butyl-4-hydroxyphenyl)propionate]
~L~L t~
2-Amino-2-(acetoxy)methyltrimethylenebis[3-~3,5-di-t~butyl-4-hydroxyphenyl)propionate]
.2-Amino-2-(hexanoyloxy)methyltrlmethylenebis[3-~3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(dodecanoyloxy)methyltrimethylenebis~3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(stearoyloxy)methyltrimethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-(benzoxy)methyltrimethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-isobutanetriyltris[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]
2-Amino-2-isobutanetriyltris[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]hydrochloride 2-Amino-2-[3-(3,5-di-t-butyl-4~hydroxyphenyl)propion-oyloxy]methyltrimethylene diacetate 2-Amino-2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-oyloxy]methyltrimethylene dihexanoate 2-Amino-2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-oyloxy]methyltrimethylene didecanoate 2-Amino-2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-oyloxy]methyltrimethylene distearate 2-Amino-2-13-(3,5-di-t-butyl-~-hydroxyphenyl)propion-oyloxy]methyltrimethylene dibenzoate Example 1 2-Amino-2-methylpropyl[3-(3,5-di-t- utyl-4-hyd oxy-~henyl)propionate].
In a 1 liter, three-neck, round-bottom flask equipped with a thermometer, stirrer and condenser were placed 66.2 g (0.2 moles) 2-[3-~3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-4,4-dimethyl-'7~
2-oxazoline, 400 ml isopropanol and 33 ml 6N hydrochloric acid.
The mixture was heated to 45C for 2 hours and then cooled.
To this stirred solution was added 250 ml of water and 33 ml of 6N sodium hydroxide. The product was removed by filtration and dried. The title compound, thus obtained, melted at 97-99C
Example 2 2-Amino isobutanetriyl tris~3-(3,5-d_-t-butyl-4-_~_roxyphenyl)propionate]
to 44.2g (0.05 moles) of 2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-2-oxazoline-4,4-dimethyl bis~3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] in 200 ml of toluene was added 8.2 ml of 6N hydrochloric acid. After the mixture was stirred for 3 hours, 6 g of sodium carbonate were added. The mixture was stirred for 15 minutes and the layers were separated.
The amine was not isolated; it was used as is in subsequent re-actions.
Example 3 2-Amino-2-ethyltrimethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)pro~ionatelhydrochloride.
In a 2 liter, three-neck, round-bottom flask equipped with a therm~ter, stirrer and condenser were placed 298g (0.48 moles) of 2-[3-(3,5-di-t-butyl-4-hydroxyphenyl~ethyl]-4-ethyl-2-oxazoline-4-methyl[3-(3/5-di-t-butyl-4-hydroxyphenyl)propion-ate], 800 ml of :isopropanol and 90 ml of 6N hydrochloric acid.
The mixture was refluxed for 4 hours. The isopropanol was re-moved and the residue was refluxed in a 2:1 mixture of hexane-toluene to remove the residual water. On cooling the product crystallized. It was removed by filtration and dried. The melting point was 144~150C.
.X
7~f~
Example 4 2-Amino-2-methyltrimethylene b~sE3-~3,s-di-t-butyl-4-hydroxyphenvl)~ropionate]hydrochloride.
The title compound was prepared as described in Ex-ample 3 except that 451 g ~0.743 mo:Les~ of 2-E2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-4-methyl-2-oxazoline-4-methyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] were used instead of 0.48 moles of 2-[2-(3,5-di~t-butyl-4-hydroxyphenyl)ethyl]-4-ethyl-2-oxazoline-4-methyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion-ate]. The title compound melted at 161-166C.
,X
Claims (10)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound having the structural formula (3-R-5-R1-4-C6H2OH)CH2CH2COOCH2C(B)(D)-K
wherein R and R1 may be the same or different and are C1-C12 alkyl; B and D may be the same or different and are hydrogen, C1-C4 alkyl, -CH2OH or -CH2OOCZ wherein Z is hydrogen, C1-C17 alkyl, phenyl or -CH2CH2(3-R-5-R1-4-C6N2OH) wherem R and R1 have the meanings above; and K is -NH2 or -NH2 ? HL wherein L
is a halogen anion.
wherein R and R1 may be the same or different and are C1-C12 alkyl; B and D may be the same or different and are hydrogen, C1-C4 alkyl, -CH2OH or -CH2OOCZ wherein Z is hydrogen, C1-C17 alkyl, phenyl or -CH2CH2(3-R-5-R1-4-C6N2OH) wherem R and R1 have the meanings above; and K is -NH2 or -NH2 ? HL wherein L
is a halogen anion.
2. A compound according to claim 1 wherein R and R1 are tertiary butyl.
3. P. process for preparing a compound of the formula of claim 1, wherein K is -NH2 ? HL comprising reacting a compound of the formula wherein B and D are defend as in claim 1, with an aqueous acid in at least a 1:1 molar ratio at a temperature of from 15 to 150°C for from 2-8 hours and at a pressure of from 100 Pa to 10kPa and in the presence of an inert solvent.
4. A process according to claim 3 wherein said acid is hydrochloric acid.
5. A process according to claim 3 wherein said solvent is isopropanol.
6. A process according to claim 3 wherein said solvent is toluene.
7. A process for preparing a compound of the formula as defined in claim 1, wherein K is -NH2 comprising reacting a compound of the formula as defined in claim 1, wherein K is -NH2 ? HL with an aqueous base in at least a 1:1 molar ratio at a temperature of from 0-25°C for a period of 1 hour and in the pre-sence of an inert solvent.
8. A process according to claim 7 wherein said bases are sodium hydroxide, sodium bicarbonate or sodium carbonate.
9. A process according to claim 7 wherein said solvent is isopropanol.
10. A process according to claim 7 wherein said solvent is toluene.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US93108778A | 1978-08-04 | 1978-08-04 | |
| US931,087 | 1978-08-04 | ||
| US4378979A | 1979-05-30 | 1979-05-30 | |
| US043,789 | 1979-05-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1157879A true CA1157879A (en) | 1983-11-29 |
Family
ID=26720821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000332528A Expired CA1157879A (en) | 1978-08-04 | 1979-07-25 | Derivatives of 2-oxazolines useful as intermediates in the preparation of antioxidants |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1157879A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8500260B2 (en) | 2011-04-27 | 2013-08-06 | Xerox Corporation | Ink compositions incorporating substituted oxazoline compounds or substituted oxazoline derivatives |
-
1979
- 1979-07-25 CA CA000332528A patent/CA1157879A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8500260B2 (en) | 2011-04-27 | 2013-08-06 | Xerox Corporation | Ink compositions incorporating substituted oxazoline compounds or substituted oxazoline derivatives |
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