Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Patent
1990-08-15
1992-07-14
Reamer, James H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
560 44, C07C22926
Patent
active
051304694
DESCRIPTION:
BRIEF SUMMARY
The present invention concerns new N-alkyl or N-acyl derivatives of N,N-bis (2,2-dimethyl-2-carboxyethyl), the manufacturing procedure and utilization of the same.
The formula of the new compounds of the invention is as follows. ##STR2## wherein R and R" are similar or different C.sub.1 -C.sub.10 -alkyl or -aryl groups, R' is a C.sub.3 -C.sub.12 -alkyl or an aralkyl group which may contain a carboxyl ester group in the carbon chain.
It is known in the art that the primary and secondary amines react with formaldehyde and isobutylaldehyde (cf. EP No. 46288 and Arch. Pharmaz. 308/75, p. 352), producing either direct-chain or cyclic Mannich reaction products (formulae 1 and 2). ##STR3##
In the present invention, the modified Mannich reaction is used as an intermediate step in the preparation of different N-alkyl- and N-acyl-derivatives of N,N-bis(2,2-dimethyl-2-carboxyethyl)amine in accordance with the following reaction formula (3-7). ##STR4## This condensation reaction (3) in which the group Y may be halide or sulphate can be accomplished at 50.degree. to 90.degree. C. in about three hours, either under refluxing conditions or under small overpressure using paraformaldehyde, trioxane or 40% of aqueous formaldehyde solution for starting material.
Thereafter, the obtained compound is oxidized as taught by formula (4): ##STR5## The oxidation reaction (4) can be performed using conventional oxidation procedures such as oxygen, ozone, peroxide, hypohalogen acids, permanganate, chromate, or dichromate oxidation. A particularly advantageous oxidation procedure is e.g. oxidation with about 50% hydrogen peroxide, which takes about three hours at 50.degree. to 75.degree. C.
The oxidized product is esterified according to the reaction (5): ##STR6## The esterification of the compound II can be accomplished using a number of conventional esterification procedure with organic or mineral acids (p-toluene sulphonic acid, HCl, etc.) as catalyst. It is particularly advantageous to use gaseous hydrochloric acid, and the reaction is accomplished at 100.degree. to 150.degree. C., with reaction times from about three to six hours.
Thereafter, the esterified product is acylated (formula 6) or alkylated (7). ##STR7## In the formulae 1-7, R and R' refer to a similar or different alkyl or aryl group with 1-12 carbon atoms, and R" refers to an alkyl or aryl group or a group which in addition to the hydrocarbon chain contains a COOR group. X refers to halogen.
The N acylation of the compound III can be performed using advantageous acid halide or anhydride. More advantageous is acylation with acid chloride at 20.degree. to 100.degree. C. for 2 to 20 hours.
The N alkylation of the compound III can be performed e.g. using the ester of 2-chloroacetic acid at 140.degree. to 150.degree. C. for 3 to 8 hours.
The compounds of type IV and V concerned in the present invention are therefore new in chemical composition, manufacturing process and applications. Their manufacture and testing in particular for uses as PVC plasticizers and stabilization are described more in detail in the following examples.
EXAMPLE 1
Item A
In a reactor, which was equipped with a mixer, a reflux condenser and a thermometer, 66.9 g ammonium chloride, 162 g formaline and 144 g isobutyraldehyde and 1 ml hydrochloric acid were charged. The mixture was heated up to 60.degree. C., whereby the isobutyraldehyde started to reflux. At the end of the refluxing the temperature was raised to 80.degree. C. at which the boiling was continued for 2.5 hrs. The condensation product (362 g) thus obtained was dissolved in acetic acid and heated to 60.degree. C., whereafter 158.1 g 47% hydrogen peroxide was added during one hour. After the addition, the mixture was boiled for 2 hours at 70.degree. to 75.degree. C. The water was evaporated from the reaction mixture, and the raw product thus obtained was recrystallized from the acetic acid-ethyl acetate mixture. The crystallized product was filtered and washed with ethyl methyl ketone-toluene mixture and petroleum ether. The melting p
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Ankner Kjell
Himanen Soile
Lahtinen Leila
Nummelin Ulf
Riutta Oili
Neste Oy
Reamer James H.
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