Production method of asymmetric copper complex crystal
A method of producing an asymmetric copper complex crystal comprising reacting an optically active salicylidene amino alcohol compound with a copper compound, then, performing a crystallization treatment in the presence of an alcohol solvent.
1. A method of producing an asymmetric copper complex crystal comprising reacting an optically active salicylidene amino alcohol compound of the formula (1):
wherein, R 1 represents an alkyl group, aryl group or aralkyl group, R 2 represents an optionally substituted alkyl group or optionally substituted phenyl group, R 3 and R 4 are the same or mutually different and represent a hydrogen atom, halogen atom, nitro group, alkyl group, fluoroalkyl group, alkoxy group, alkoxycarbonyl group, trialkylsilyl group or cyano group, and * represents that the carbon atom is an optically active point with a copper compound, then, performing a crystallization treatment in the presence of an alcohol solvent, wherein the optically active salicylidene amino alcohol compound of the formula (1) is a compound obtained by reacting an optically active amino alcohol compound of the formula (2):
with a salicylaldehyde compound of the formula (3):
wherein the optically active amino alcohol compound of the formula (2) is a compound obtained by reacting an optically active amino acid ester compound of the formula (4):
wherein, R 1 and * represent the same meanings as described above, and R 5 represents an optionally substituted alkyl group or optionally substituted phenyl group with a Grignard compound of the formula (5):
R 2 —MgX (5)
wherein R 2 represents the same meanings as described above, and X represents a halogen atom,
and wherein the optically active amino acid ester compound of the formula (4) is a compound obtained by treating an addition salt of the optically active amino acid ester compound and an acid with a tertiary amine compound base.
2. The production method according to claim 1 , wherein the alcohol solvent is methanol.
3. The production method according to claim 1 , wherein the copper compound is a divalent copper compound.
4. The production method according to claim 3 , wherein the divalent copper compound is copper(II) acetate or copper(II) hydroxide.
5. The production method according to claim 3 , wherein the divalent copper compound is copper(II) acetate.
6. The production method according to claim 1 , wherein X in the formula (5) is a bromine atom.
7. The production method according to claim 1 , wherein the tertiary amine compound is triethylamine.
8. A method of producing an asymmetric copper complex crystal comprising reacting an optically active salicylidene amino alcohol compound of the formula (1):
wherein, R 1 represents an alkyl group, aryl group or aralkyl group, R 2 represents an optionally substituted alkyl group or optionally substituted phenyl group, R 3 and R 4 are the same or mutually different and represent a hydrogen atom, halogen atom, nitro group, alkyl group, fluoroalkyl group, alkoxy group, alkoxycarbonyl group, trialkylsilyl group or cyano group, and * represents that the carbon atom is an optically active point with a copper compound, then, performing a crystallization treatment in the presence of an alcohol solvent, wherein the optically active salicylidene amino alcohol compound of the formula (1) is a compound obtained by reacting an optically active amino alcohol compound of the formula (2):
with a salicylaldehyde compound of the formula (3):
wherein the optically active amino alcohol compound of the formula (2) is a compound obtained by reading an optically active amino acid ester compound of the formula (4):
wherein, R 1 and * represent the same meanings as described above, and R 5 represents an optionally substituted alkyl group or optionally substituted phenyl group with a Grignard compound of the formula (5):
R 2 —MgX (5)
wherein R 2 represents the same meanings as described above, and X represents a halogen atom,
and wherein the optically active amino acid ester compound of the formula (4) is a compound obtained by treating an addition salt of the optically active amino acid ester compound and an organic sulfonic acid compound with a base.
9. The production method according to claim 8 , wherein the organic sulfonic acid compound is p-toluenesulfonic acid.
10. The production method according to claim 1 , wherein the temperature for treatment of an addition salt of the optically active amino acid ester compound of the formula (4) and an acid with a base is in the range of 0 to 10° C.
11. The production method according to claim 1 , wherein R 1 in the formula (1) is an alkyl group having 1 to 4 carbon atoms.
12. The production method according to claim 1 , wherein R 1 in the formula (1) is a methyl group.
13. The production method according to claim 1 , wherein R 2 in the formula (1) is an optionally substituted phenyl group.
14. The production method according to claim 1 , wherein R 2 in the formula (1) is a 2-n-butoxy-5-tert-butylphenyl group.
15. The production method according to claim 1 , wherein R 3 is a hydrogen atom and R 4 is a nitro group in the formula (1).
16. The production method according to claim 15 , wherein the nitro group represented by R 4 in the formula (1) is linked to the 5-position on the connected phenyl group.