Process for the preparation of benzaldehydes

• US 5,082,976 A
• Filed: 10/25/1990
• Issued: 01/21/1992
• Est. Priority Date: 12/01/1989
• Status: Expired due to Fees

• Current Assignee: Helmut Kraus
• Original Assignee: Bayer AG
• Inventors: Kraus, Helmut, Blank, Heinz U.
• Primary Examiner(s): LONE, WERREN
• Application Number:
  US07/603,110
• Time in Patent Office: 453 Days
• Field of Search: 568/41, 568/27, 568/28, 568/32, 568/33, 568/423, 568/431, 568/437, 568/436
• US Class Current: 568/431
• CPC Class Codes: C07C 201/12 by reactions not involving the formation of nitro groups
• CPC Class Codes: C07C 205/44 the carbon skeleton being further substituted by —CHO groups
• CPC Class Codes: C07C 253/30 by reactions not involving the formation of cyano groups
• CPC Class Codes: C07C 255/56 containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
• CPC Class Codes: C07C 255/57 containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton

Abstract

Benzaldehydes of the formula ##STR1## can be obtained by reaction of substituted β-amino-styrenes of the formula ##STR2## in which R¹, R², R³, R⁴, R⁵, R⁸, R⁹, R¹⁰, m, n and o have the scope of meaning indicated in the description, with oxygen in the presence of a Cu compound in the solution of an aprotic polar solvent at 0°-120° C.

Claims

1. Process for the preparation of a benzaldehyde which carried an electron-withdrawing substituent in at least one of the ortho- and para-positions, of the formula ##STR14## in which R¹, R² and R³ independently of one another denote nitro, cyano, COOR⁶, SO₂ --OR⁵ or SO₂ --R⁵,

represents hydrogen, straight-chain or branched C₁ -C₈ -alkyl, straight-chain or branched C₁ -C₈ -alkoxy, phenyl, benzyl, cyclopentyl, cyclohexyl, fluorine, chlorine, bromine or --N(R⁶,R⁷),

denotes hydrogen or the aldehyde group --CHO,

where

R⁶ and R⁷ independently of one another denote straight-chain or branched C₁ -C₄ -alkyl, benzyl or phenyl,

where, furthermore, the cyclic substituents mentioned may in turn be substituted once or twice by methyl, ethyl, methoxy, ethoxy, fluorine, chlorine or bromine and m, n and o independently of one another can assume the value zero or one, but the sum m+n+o is limited to the value one or two,

wherein a substituted β

-amino-styrene of the formula ##STR15## in which R¹, R², R³, R⁴, m, n and o have the meaning mentioned,

R⁸ and R⁹ independently of one another denote straight-chain or branched C₁ -C₈ -alkyl, C₅ -C₇ -cycloalkyl, straight-chain or branched C₂ -C₈ -alkenyl, straight-chain or branched C₂ -C₈ -alkoxyalkyl, straight-chain or branched C₃ -C₈ -alkoxyalkenyl, C₆ -C₁₂ -aryl, C₇ -C₁₀ -aralkyl or a 5- to 8-membered saturated or unsaturated heterocyclic ring whose heteroatoms are one or two of the group comprising N, O and S,

where furthermore

R⁸ and R⁹, together with the N atom which they substitute, form a 5- to 8-membered saturated or unsaturated, non-aromatic N-heterocyclic ring which contain a further heteroatom from the group comprising N, O or S, and

R⁸ additionally denotes hydrogen,

R⁹ additionally denotes the group ##STR16## in which p assumes the value 2, 3 or 4, and

R¹⁰ denotes hydrogen or the group ##STR17## or a mixture of several of such β

-amino-styrenes which differ is reacted with oxygen in the presence of an anhydrous copper salt in the solution of an aprotic, polar solvent selected from the group comprising dimethylformamide (DMF), dimethylacetamide, diethylformamide, diethylacetamide, hexamethylphosphoramide, acetone, methyl ethyl ketone, methyl tert.-butyl ketone, dimethyl sulphoxide, acetonitrile, propionitrile, N-methylpyrrolidone (NMP), N-methyl-caprolactam (NMC) and N,N-dimethyl-imidazolidinone (DMI), at 0°

-120°

C.

2. The process of claim 1, wherein the reaction with oxygen is carried out at 20°

-100°

C.

3. The process of claim 2, wherein the reaction with oxygen is carried out at 30°

-80°

C.

4. The process of claim 1, wherein a substituted β

-amino-styrene of the formula ##STR18## is reacted, in which R⁸, R⁹, m, n and o have the meaning mentioned in claim 1, p1 R¹¹, R¹² and R¹³ independently of one another represent nitro or cyano and

R¹⁴ denotes hydrogen, straight-chain or branched C₁ -C₄ -alkoxy, fluorine, chlorine or bromine.

5. The process of claim 4, wherein a substituted β

-amino-styrene of the formula ##STR19## is reacted, in which R¹¹, R¹², R¹³, R¹⁴, m, n and o have the meaning mentioned in claim 4 and

R¹⁸ and R¹⁹ independently of one another denote straight-chain or branched C₁ -C₈ -alkyl, phenyl, benzyl, cyclohexyl or a 5- to 6-membered saturated heterocyclic ring which contains a N or O as heteroatom,

where furthermore

R¹⁸ and R¹⁹, together with the N atom which they substitute, form a 5- to 6-membered N-heterocyclic ring which contains a further heteroatom from the group comprising N and O.

6. The process of claim 5, wherein a substituted β

-amino-styrene of the formula ##STR20## is reacted, in which R¹¹, R¹², R¹³, R¹⁴, m, n and o have the meaning mentioned in claim 5 and

R²⁸ and R²⁹ independently of one another denote straight-chain or branched C₁ -C₄ -alkyl, benzyl or cyclohexyl,

where furthermore

R²⁸ and R²⁹, together with the N atom which they substitute, form the pyrrolidine ring, the oxazolidine ring, the piperidine ring, the piperazine ring or the morpholine ring.

7. The process of claim 6, wherein a substituted β

-amino-2-nitro-styrene of the formula ##STR21## is reacted, in which R¹⁴, R¹⁸ have the scope mentioned in claim 5.

8. The process of claim 1, wherein the substituted β

-amino-styrene is employed in the form of the crude product form the aminomethylenation of the underlying substituted toluene.

9. The process of claim 1, wherein as the aprotic polar solvent, a substituted acid amide selected from the group comprising dimethylformamide, dimethylacetamide, diethylformamide, diethylacetamide, and hexamethylphosphoramide or a ketone or a sulphoxide is employed, which can be replaced by an inert solvent up to 5-50% by weight, relative to the total amount of solvent.

10. The process of claim 9, wherein a substituted acid amide selected from the group comprising dimethylformamide, dimethylacetamide, diethylformamide, diethylacetamide, and hexamethylphosphoramide is employed as the aprotic polar solvent.

11. The process of claim 10, wherein dimethylformamide is employed as the aprotic polar solvent.

12. The process of claim 9, wherein as the aprotic polar solvent, the solvent from the preceding amino-methylenation is employed in the form of the crude reaction mixture obtained in this case.

13. The process of claim 1, wherein a Cu(I)salt is employed as the Cu compound.

14. The process of claim 13, wherein a Cu(I)halide is employed as the Cu compound.

15. The process of claim 1, wherein the Cu compound is employed in an amount of 1-200 mol-%, relative to the substituted β

-amino-styrene.

16. The process of claim 15, wherein the Cu compound is employed in an amount of 5-40 mol-%, relative to the substituted β

-amino-styrene.

17. The process of claim 16, wherein the Cu compound is employed in an amount of 10-20 mol-%, relative to the substituted β

-amino-styrene.