Patent GB-708523-A (GB)
Title: Improvements in and relating to the production of nitrogen and oxygen containing heterocyclic compounds having emulsifying, detergent and wetting properties and to compositions thereof with surface active agents
Inventor: BAUER EMILE
IPC: C07D295/088
Filed: 1950-07-31
Abstract: Oxazines of the formula <FORM:0708523/IV (b)/1> in which R is an acyl radical R1CO or consists of an acyloxy radical R1CO-O- connected to the N atom by a chain of at least two carbon atoms, R1 being an organic radical containing at least 11 atoms of carbon while X1 and X2 each represent one or two CH2 groups, are obtained from the corresponding substituted amino alcohol <FORM:0708523/IV (b)/2> (obtained by heating together at a suitable temperature the corresponding amino alcohol and a carboxylic acid R1COOH or a functional derivative thereof) by heating the said substituted amino alcohol to a temperature higher than said temperature to which the said reactants have been heated to form the substituted amino alcohol whereby the latter loses one molecular proportion of water to form the oxazine.  The substituted amino alcohols are preferably derived from di- or tri-ethanolamine and di- or tri-propanolamine, and acids such as lauric, stearic, elaidic, palmitic, oleic, ricinoleic or abietic acids.  The temperature at which the oxazine is formed may be between 180 DEG  and 280 DEG  C., and the heating may, if desired, be carried out in the presence of a dehydration catalyst such as a mineral acid, e.g. sulphuric acid, sulphamic acid, or a sulphonic acid, e.g. butyl naphthalene sulphonic acid.  Certain of the products have emulsifying, detergent, wetting, dispersing, softening, bactericidal and insecticidal properties and when the products are mixed with surface-active agents they impart properties of solubility and an emulsive power for vegetable, animal, or mineral oils (see Group III).  In examples: (1) oleic acid and triethanolamine are heated together at between 180 DEG  and 200 DEG  C. until one molecular proportion of water is eliminated, thus yielding an ester of triethanolamine which is then heated at between 230 DEG  and 260 DEG  C. until a further molecular proportion of water is removed, thereby forming the oxazine.  The salt of the latter with formic or acetic acid is an excellent emulsifying agent whilst sulphonation of the oxazine followed by neutralization with caustic soda yields a product having good dispersing and detergent properties; (2) 1/3 molecular proportion of castor oil is heated at between 180 DEG  and 200 DEG  C. with one molecular proportion of triethanolamine to yield the ester which is a weak base that can form a salt with acids, the ester is then heated in the presence of sulphuric acid to yield the oxazine which gives a salt with acetic acid having good wetting, dispersing and softening properties.  When the base is sulphonated and neutralized with caustic soda the product has good wetting properties and is stable to water-hardening agents; (3) oleic acid is heated with diethanolamine at 170-190 DEG  C. until one molecular proportion of water is eliminated and the amide product is then heated at 230-260 DEG  C. in the presence of sulphamic acid until the product loses a further molecular proportion of water to form an oxazine.  The latter on sulphonation followed by neutralization with soda yields a product having excellent emulsifying, detergent, and dispersing properties; (4) abietic acid and triethanolamine are heated at 180-200 DEG  C. in the presence of sulphuric acid under a reduced pressure of 50 mm. of mercury to yield the abietic ester of triethanolamine which gives an easily soluble salt with an organic ester and the ester is then heated to between 230 DEG  and 260 DEG C. to eliminate a further molecular proportion of water to yield the oxazine which in the form of its formic acid salt has excellent emulsifying and washing properties; (5) the methyl ester of lauric acid is heated with triethanolamine at 180-200 DEG  C. to form the ester which is then heated to 230-260 DEG  C. in the presence of butyl naphthalene sulphonic acid until one molecular proportion of water is eliminated to yield the oxazine which is a weak base; (6) elaidic acid is heated with triethanolamine at 180-200 DEG  C. until one molecular proportion of water is eliminated, thus giving the ester which is then heated to 230-260 DEG  C. until a further molecular proportion of water is lost and an oxazine formed.  When the latter is sulphonated with acetyl sulphuric acid and then neutralized with caustic soda it forms an excellent detergent, dispersing and emulsifying agent which is resistant to water-hardening agents; (7) oleic acid chloride is heated with triethanolamine and the ester product obtained is then heated to between 230 DEG  and 260 DEG  C. to form the oxazine the salt of which with formic or acetic acid is an excellent emulsifying, detergent and dispersing agent.  Reference is also made to the oxazine products obtained from triethanolamine and ricinoleic acid and triethanolamine and pea-nut oil.ALSO:An emulsifying composition consists of a mixture of a surface active agent with an oxazine having the formula <FORM:0708523/III/1> in which R is an acyl radical R1CO or consists of an acyloxy radical R1COO connected to the N atom by a chain of at least two carbon atoms, R1 being an organic radical containing at least 11 atoms of carbon while X1 and X2 each represent one or two CH2 groups, the oxazine being obtained from the corresponding substituted amino alcohol <FORM:0708523/III/2> (obtained by heating together at a suitable temperature the corresponding amino alcohol and a carboxylic acid R1COOH or a functional derivative thereof) by heating the said substituted amino alcohol to a temperature higher than the said temperature to which the said reactants have been heated to form the substituted amino alcohol whereby the latter loses one molecular proportion of water to form the oxazine (see Group IV (b)).  The substituted amino alcohols are preferably derived from di- or tri-ethanolamine or di- or tri-propanolamine and acids such as lauric, stearic, elaidic, palmitic, oleic, ricinoleic or abietic acids.  In examples: (1) sodium tributylnaphthalene sulphonate is mixed with the oxazine obtained from triethanolamine and oleic acid to yield a pulp which is completely soluble in mineral and vegetable oils and gives stable aqueous emulsions having a very fine state of subdivision, whereas the oxazine alone dissolved in the mineral or vegetable oils yields unstable aqueous emulsions; (2) the oxazine obtained by esterification of peanut oil with triethanolamine and then heating the resulting ester is mixed with the product formed by condensation of castor oil with a polyglycol having at least 12 atoms of carbon and the oily mixture formed dissolves in mineral and vegetable oils and gives stable and finely divided water-emulsions; (3) oleic sulphonate is mixed with a portion of the oxazine obtained from triethanolamine and ricinoleic acid and the mixture gives stable and finely divided aqueous emulsions with mineral and vegetable oils.