This invention relates to a novel process for the preparation of hydroxylated primary amines. More particularly, this invention relates to a novel process for the preparation of hydroxylated primary amines having the formula: EQU R--X--CH.sub.2 --CH(OH)--CH.sub.2 NH.sub.2 (I)
in which R represents a saturated or ethylenically or acetylenically unsaturated straight-chain C.sub.5 -C.sub.18 aliphatic radical and X represents --O--, --S--, --NH-- or --CH.sub.2 --, preferably an oxygen or sulfur atom and the hydrohalide, acetate and quaternary alkyl ammonium salts of these compounds. These compounds are known and are disclosed in Rancurel, et al, U.S. Pat. No. 4,196,217. The nonyl, decyl and dodecyl radicals are mentioned in particular as examples of a saturated aliphatic radical which may be represented by the radical R. These compounds, and particularly the compound of formula (I) in which R is the decyl radical and X is oxygen, i.e., 1-amino-3- decyloxy-2-propanol in the form of its hydrochloride, hydrobromide or acetate salt, are disclosed as being useful as sterilizing agents, preservatives and antiseptics.
Rancurel et al, U.S. Pat. No. 4,196,217, disclose that the compounds of formula (I) in which X is sulfur or oxygen can be prepared by the following process: ##STR3##
In these formulas, X represents --O-- or --S--, R has the same meaning as in formula (I) and R.sub.1 and R.sub.2 together represent an epoxy radical or R.sub.2 represents a hydroxy radical and R.sub.1 is a halogen atom, preferably chlorine or bromine.
The reaction of equation (1) is carried out in the presence of a compound, such as potassium or sodium carbonate, which is capable of making the phthalimide react in the form of its sodium or potassium derivative.
The hydrolysis reaction (2) is carried out in the presence of hydrochloric acid.
The compounds of formula (II) are known compounds as are methods for their preparation and may be prepared, for example, by reacting an epihalohydrin: ##STR4## with an alcohol in the presence of a catalyst, such as stannic chloride, zinc chloride, ferric chloride, the boron fluoroetherate complex or tosylic acid. The product obtained is a halogenated alcohol.
The epoxide of formula (II) may be prepared by cyclizing the above halogenated alcohol or by other known methods.
Rancurel et al, in U.S. Pat. No. 4,196,217 also disclose that the compounds of formula (I) can be prepared by reacting ammonia or an amine such as triethylamine with a halogenated alcohol of formula (II) or with an epoxide of formula (II). However, Rancurel et al, state that these reactions generally result in the formation of a mixture of amines in addition to the desired primary amine. For example, when using ammonia, the primary amine product is a better nucleophile than ammonia and can compete effectively for starting material leading to the formation of secondary and tertiary amines in addition to the desired primary amine product. Similarly, the use of primary amines results in mixtures of secondary and tertiary amine products. This lack of selectivity makes these routes unattractive commercially. Further, production of the compounds of formula (I) by the Gabriel synthesis route disclosed by Rancurel et al involves the use of phthalimide which is expensive and hydrazine which is used to hydrolyze the first formed N-alkylphthalimide making this route not only commercially unattractive from the standpoint of cost but also dangerous due to the toxicity and potential explosiveness of hydrazine.
K. S. Laurenzo in U.S. Ser. No. 269,363 filed Nov. 10, 1988 discloses a method for preparing the hydrohalide and acetate salts of the hydroxylated amines of formula (I) in high yields and at reduced cost without the need for using costly phthalimide or potentially dangerous hydrazene by reacting an expoxide of formula (II) with ammonium carbamate to form the corresponding substituted ammonium carbamate and thereafter lU forming the corresponding hydrohalide or acetate salt of the substituted ammonium carbamate by conventional techniques such as, for example, by contacting the substituted ammonium carbamate with gaseous or aqueous hydrogen chloride or hydrogen bromide or, in the case of the acetate, reacting the substituted ammonium carbamate with acetic acid. This represents a substantial advance in the art.
USPTO Backgrounds
USPTO Backgrounds