Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2000-05-02
2001-09-11
Padmanabhan, Sreeni (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S265000, C568S433000
Reexamination Certificate
active
06288276
ABSTRACT:
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable.
BACKGROUND OF THE INVENTION
Ortho-formylated phenols and their derivatives are valuable intermediates in the preparation of products for the chemical, pharmaceutical and mining industries. Therefore, processes for making hydroxyarylaldehydes, and in particular, 2-hydroxyarylaIdehydes, have been well researched. It is well recognized that such hydroxyarylaldehydes can be made by reacting magnesium phenoxides with formaldehyde under anhydrous conditions.
SUMMARY OF THE INVENTION
The present invention relates to an oxime of the formula IV, a process for making an oxime of the formula IV, an aryloxy magnesium salt of the formula II, a process for making an aryloxy magnesium salt of the formula II and a process for making an aidehyde of the formula III
The process for making an oxime of the formula IV
wherein each of R
2
-R
5
is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms comprises the steps of: (1) reacting a compound of the formula I
wherein each of R
1
-R
5
is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms with the proviso that one of R
1
-R
5
is hydrogen with magnesium alkoxide to form an aryloxy magnesium compound: (2) reacting the aryloxy magnesium compound with a compound capable of forming a non-aryloxy anion X to form a compound of the formula II wherein X is a non-aryloxy anion selected from the group consisting of chloride, acetate, sulfate, nitrate, sulfonate, hydroxide, oxide, carboxylate, formate; N is an integer having a value of 1 or 2; each of R
1
-R
5
is defined as above to form an aryloxy magnesium salt of the formula II;
(3) reacting a compound of the formula II with formaldehyde to yield an aldehyde of the formula III
(4) reacting a compound of the formula III with hydroxylamine to produce an oxime of the formula IV.
The process for making an aryloxy magnesium salt of the formula II
comprises reacting a compound of the formula I
wherein each of R
1
-R
5
is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms with magnesium alkoxide to form an aryloxy magnesium compound; (2) reacting the aryloxy magnesium compound with a compound capable of forming a non-aryloxy anion X wherein X is a non-aryloxy anion selected from the group consisting of chloride, acetate, sulfate, nitrate, sulfonate, hydroxide, oxide, carboxylate, formate; N is an integer having a value of 1 or 2; and each of R
1
-R
5
is defined as above.
The process for making an aldehyde of the formula III comprises (1) reacting a compound of the formula I
wherein each of R
1
-R
5
is defined as above with magnesium alkoxide to form an aryloxy magnesium salt of the formula II;
(2) reacting the aryloxy magnesium compound with a compound capable of forming a non-aryloxy anion X to form a compound of the formula II wherein X is a non-aryloxy anion selected from the group consisting of chloride, acetate, sulfate, nitrate, sulfonate, hydroxide, oxide, carboxylate, formate; N is an integer having a value of 1 or 2; each of R
1
-R
5
is defined as above with the proviso that one of R
1
or R
5
is hydrogen; (3) reacting a compound of the formula II with formaldehyde to yield an aldehyde of the formula III
Unlike similar methods which employ non-aryloxy anions, step (3) above can be carried out in the presence of water.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
Not Applicable.
DETAILED DESCRIPTION OF THE INVENTION
The oximes according to the invention are compounds of the formula IV
wherein each of R
2
-R
5
is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms. These compounds, which can be made by the processes disclosed herein, are useful as extractants for metals from aqueous solutions such as from aqueous acid leach solutions in metal recovery operations. The preferred compounds of formula IV are those wherein R
3
is a dodecyl group or a nonyl group and each of R
2
, R
4
and R
5
is hydrogen.
The aryloxy magnesium salts according to the invention are those of the formula II
wherein each of R
2
-R
5
is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms. The aryloxy magnesium salts are useful as intermediates in the production of the aldehydes of formula III and the oximes of formula IV as disclosed herein. The preferred aryloxy magnesium salts are those in which R
3
is a dodecyl or a nonyl group; R
3
is a dodecyl group and each of R
2
, R
4
and R
5
hydrogen; R
3
is a nonyl group, each of R
2
, R
4
and R
5
hydrogen and X is an acetate ion or a chloride ion.
The processes according to the invention begin with the formation of the aryloxy magnesium salt of the formula II. This compound can be made by reacting a phenolic compound of the formula I wherein at least one of the ortho positions, i.e. the 2- and/or 6-positions of the aromatic ring with respect to the carbon carrying the phenolic hydroxyl group, are free. That is, they are bonded to hydrogen. The other four positions in the aromatic nucleus may carry substituents which are inert under the reaction conditions. Suitable examples of such substituents include one or more of hydrogen atoms; halogen atoms; alkyl, cycloalkyl, and alicyclic groups, aryl groups, alkaryl groups, aralkyl groups having 1-36 carbon atoms; alkoxy groups, aryloxy groups which have from 1-30 carbon atoms; acyl groups which have from 1-24 carbon atoms; and any combinations thereof. Such compounds can be prepared by any of the methods known to those skilled in the art.
The aryloxy magnesium salt of the formula II is made from an arlyoxy magnesium intermediate. The arlyoxy magnesium intermediate can be prepared by any of the methods known to those skilled in the art. Such methods include, for example, reacting magnesium in the form of its alkoxide, e.g. methoxide, with a reactant capable of providing the aryloxy group, i.e. a phenolic compound, such as e.g. para-nonyl phenol, in the presence of a non-polar solvent such as e.g. benzene, toluene, xylene or cyclohexane optionally in the presence of a polar co-solvent. Examples of polar cosolvents that may be used include one or more of: lower C1-C4 alcohols such as, e.g., methanol and ethanol; amines such as e.g. triethylamine or pyridine; amides such as, e.g., dimethylformamide and N,N-dimethylacetamide; sulfoxides such as, e.g., dimethyl sulfoxide; mono-glyme, di-glyme and tri-glyme; and ethers such as, e.g., diethyl ether, diphenyl ether and tetrahydrofuran. The reaction mixture is heated to reflux to allow the magnesium to dissolve. The phenolic compound, e.g. nonyl phenol, is then added to this solution of magnesium alkoxide in a non-polar solvent with agitation to ensure good mixing of the reactants. The mixture is suitably heated for a period to facilitate completion of the reaction. The temperature for this step is preferably within the range from 25° C. to the boiling point of the reaction mixture. The reaction is preferably run at or near the boiling point of the solvent used for the reaction. For example, if toluene is used as the solvent and magnesium methoxide is the alkoxide, the reaction mixture is prefera
Chambless William H.
Dimmit Jeffrey H.
Kearns Mark A.
Drach John E.
Henkel Kommanditgeselschaft auf Aktien
Millson, Jr. Henry E.
Padmanabhan Sreeni
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