The Dow Chemical Company

Mark E Kaiser

Peter W Owen

Harry A Smith

David L Larson

Sandra Berazosky

2-H-2-Oxazolines are prepared by contacting in liquid phase a N-(.beta.-hydroxyalkyl)formamide with a small but catalytic amount of an inorganic zinc salt at elevated temperatures. Similarly, 2-substituted-2-oxazolines are prepared by contacting N-(2-hydroxyalkyl)carboxamides with a small but catalytic amount of an inorganic zinc salt. As an example, 2-H-2-oxazoline was prepared in approximately 72 percent yield by warming a mixture of N-(.beta.-hydroxyethyl)formamide with a catalytic amount of zinc chloride at a temperature of from 180.degree. C. to 185.degree. C./50 mm Hg for 2.2 hours. In this reaction, the desired oxazoline product was recovered as a codistillate with water during the course of the reaction.

Liquid phase preparation of 2-H-2-oxazolines and

2-Substituted-2-oxazolines are prepared by contacting N-(2-hydroxyalkyl)carboxamides with a small but catalytic amount of an organic zinc salt at an elevated temperature.

Preparation of 2-substituted-2-oxazolines with organic zinc salt

A cyclodehydration reaction is described for preparing 2-oxazolines which comprises reacting in liquid phase (a) an N-(2-hydroxyalkyl)carboxamide with (b) a small but catalytic amount of an iron-containing compound. The reaction is normally conducted at elevated temperatures (e.g., 180.degree.-200.degree. C.) and under reduced pressure. Both 2-H- and 2-substituted-2-oxazolines are prepared by this process. For example, 2-H-2-oxazoline and 2-ethyl-2-oxazoline were prepared in 83.1 percent and 90.2 percent yields, respectively, by contacting the appropriate N-(2-hydroxyethyl)carboxamide with ferrous chloride tetrahydrate at temperatures of approximately 180.degree.-200.degree. C./50 mm Hg. Under these conditions, the oxazoline product and water were codistilled from the reaction mixture essentially as fast as they were formed.

Process for preparing 2-oxazolines

The title compounds are of the formula: ##STR1## wherein R is a chemical bond, oxygen, sulfur, alkylene or alkylidene; W is hydrogen or a (--CR.sub.1 R.sub.2 --CR.sub.3 R.sub.4 --NHR.sub.5) group with the proviso that at least two W groups are (--CH.sub.1 R.sub.2 --CR.sub.3 R.sub.4 --NHR.sub.5) groups; wherein R.sub.1 -R.sub.4 are each independently hydrogen, lower alkyl or hydroxy-substituted lower alkyl; R.sub.5 is hydrogen or a ##STR2## group, wherein R.sub.6 is hydrogen, hydrocarbyl or inertly substituted hydrocarbyl; X, Y and Z are each independently inert substituents; m and p are each independently integers of from zero to four, inclusive; n is an integer of from zero to three, inclusive; q is a number of from zero to about ten; and M is alkylene or alkylidene. They are conveniently prepared by reacting a 2-oxazoline of the formula: ##STR3## with a polyhydric polyphenol of the formula: ##STR4## in the presence of certain metal salt catalysts (e.g. zinc acetate).

Novel 2-amido- or 2-amino-alkyl ethers of polyhydric polyphenols and

N-(2-mercaptoethyl)alkanamides are produced by reacting hydrogen sulfide with 2-H-2-oxazolines or 2-alkyl-2-oxazolines. For example, N-(2-mercaptoethyl)acetamide was prepared in excellent yields by incrementally adding 2-methyl-2-oxazoline to a stirred solution of hydrogen sulfide in methanol under autogeneous pressure at about 100.degree. C.

N-(2-mercapto-ethyl)alkanamides from H.sub.2 S and 2-H-2-oxazolines or

Process for making beta-aminoethyl sulfides from aliphatic mercaptans

N-(2-alkoxyethyl)alkanamides, such as N-(2-ethoxyethyl)ethanamide and N-(2-methoxyethyl)propanamide, are prepared by reacting a 2-oxazoline with methanol or ethanol in the presence of a strong base, such as sodium methoxide. Subsequent hydrolysis of such amides provides a convenient means for obtaining 2-alkoxyethyl amines.

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Midland, MI, United States of America

Mark E Kaiser