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WO2001044162A1 - Process for the preparation of secondary and tertiary amines - Google Patents

Process for the preparation of secondary and tertiary amines Download PDF

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Publication number
WO2001044162A1
WO2001044162A1 PCT/US2000/026581 US0026581W WO0144162A1 WO 2001044162 A1 WO2001044162 A1 WO 2001044162A1 US 0026581 W US0026581 W US 0026581W WO 0144162 A1 WO0144162 A1 WO 0144162A1
Authority
WO
WIPO (PCT)
Prior art keywords
palladium
process according
ferrocene
methyl
ligand
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2000/026581
Other languages
French (fr)
Inventor
Sue L. Lin
Weixia M. Zhou
George W. Matcham
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celgro
Original Assignee
Celgro
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BR0016348-1A priority Critical patent/BR0016348A/en
Priority to HU0203901A priority patent/HUP0203901A3/en
Priority to IL14980700A priority patent/IL149807A0/en
Priority to AU77243/00A priority patent/AU7724300A/en
Priority to PCT/US2000/026581 priority patent/WO2001044162A1/en
Priority to JP2001545251A priority patent/JP2004507443A/en
Priority to NZ519366A priority patent/NZ519366A/en
Priority to CA002394519A priority patent/CA2394519A1/en
Application filed by Celgro filed Critical Celgro
Priority to KR1020027007564A priority patent/KR20020073140A/en
Priority to EP00966976A priority patent/EP1237844A1/en
Priority to MXPA02005810A priority patent/MXPA02005810A/en
Publication of WO2001044162A1 publication Critical patent/WO2001044162A1/en
Priority to FI20020955A priority patent/FI20020955A7/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

N,N-disubstituted amines in which the amino nitrogen atom is bound to the carbon of an aromatic ring disubstituted in the positions ortho to the carbon atom, are prepared by allowing a primary amine and a compound in which an ortho, ortho-disubstituted aromatic compound carrying a nucleofuge substituent, to react in a basic environment in the presence of a catalytic palladium(0) complex and a ligand, the ratio of palladium complex to ligand being greater than at least 1:1. A typical embodiment involves the reaction of 2-methyl-6-ethylphenyl-trifluoromethylsulfonate and (S)-1-methoxy-2-aminopropane in the presence of bis(dibenzylideneacetone)palladium, tri-tert.-butylphosphine, and sodium tert.-butoxide to yield (S)-N-(1-methoxyprop-2-yl)-2-methyl-6-ethylphenylamine.

Claims

1. A process for the preparation of an N,N-disubstituted or N,N,N-trisubstituted amine in which in one of the substituents the amino nitrogen atom is bound to the carbon atom of an aromatic ring disubstituted in the positions ortho to said carbon atom, which process comprises allowing (i) a primary or secondary amine and (//) a compound in which said carbon atom of the ortho, ortho-disub- stituted aromatic ring is bound to a nucleofuge, to react in a basic environment in the presence of (Hi) a catalytic palladium(O) or nickel complex and (/V) a ligand in which the ratio of palladium(O) or nickel complex to ligand is greater than at least 1 :1.
2. The process according to claim 1 wherein the reaction is conducted in an inert organic solvent.
3. The process according to claim 1 wherein a catalytic palladium(O) complex is employed and the ratio of palladium(O) complex to ligand is at least 4:1.
4. The process according to claim 1 wherein a catalytic palladium(O) complex is employed and the ratio of palladium(O) complex to ligand is at least 4:1.
5. The process according to claim 1 wherein the nucleofuge is the iodo, bromo, chloro, methanesulfonato, or trifluoromethanesulfonato radical.
6. The process according to claim 1 wherein said primary or secondary amine is an unsubstituted or substituted monoalkylamine.
7. The process according to claim 6 wherein said unsubstituted or substituted monoalkylamine is chiral.
-7-
8. The process according to claim 6 wherein said unsubstituted or substituted monoalkylamine is 1-methoxy-2-aminopropane.
9. The process according to claim 8 wherein said 1-methoxy-2-aminopropane is (S)-1-methoxy-2-aminopropane.
10. The process according to claim 1 wherein said aromatic ring is disubstituted by the same or different alkyl groups in the ortho positions.
11. The process according to claim 1 wherein the compound in which said car- bon atom of the ortΛo,ort/7θ-disubstituted aromatic ring is bound to a nucleo- fuge is 2,6-dimethylphenyl bromide, 2,6-dimethylphenyl chloride, 2,6-dimethyl- phenyl iodide, 2,6-dimethylphenyimethylsulfonate, 2,6-dimethylphenyltri- fluoromethylsulfonate, 2-methyl-6-ethylphenyl bromide, 2-methyl-6-ethylphenyl chloride, 2-methyl-6-ethylphenyl iodide, 2-methyl-6-ethylphenylmethylsulfon- ate, 2-methyl-6-ethylphenyltrifluoromethylsulfonate, 2,6-diethylphenyl bromide, 2,6-diethylphenyl chloride, 2,6-diethylphenyl iodide, 2,6-diethylphenylmethyl- sulfonate, or 2,6-diethylphenyltrifluoromethylsulfonate.
12. The process according to claim 1 wherein the catalytic palladium(O) or nickel complex is palladium chloride, palladium acetate, D/s( rat7s,frans-dibenzyl- ideneacetone)palladium, [1 ,1'-b/'s(diphenylphosphino)ferrocene]dichloropalla- dium, b/s(triphenylphosphino)dichloropalladium, tefra/ /s(triphenylphosphine)- palladium, b/s(triphenylphosphino)dichloronickel, nickelcarbonyl, or b/'s(1,5- cyclooctadiene)nickel.
13. The process according to claim 12 wherein the catalytic palladium(O) or nickel complex is 6 s(dibenzylideneacetone)palladium or tefra /s(triphenyl- phosphine)palladium.
-8-
14. The process according to claim 1 wherein the ligand is tri-(tetf.-but- yl)phosphine, 1 ,1,-b/s(diphenylphosphino)ferrocene, 2,2'-b/s(diphenylphos- phino)-1 ,1'-binaphthyl, tri-(o-tolyl)phosphine, 4,12-b/s(diphenylphosphanyl)- [2.2]paracyclophane, 1 ,1'-b/s(di-p-methoxyphenylphosphino)ferrocene, 1 ,1'- b/s(di-p-trifluoromethylphenylphosphino)ferrocene, 1 ,1'-i)/s(ditolylphosphino)- ferrocene, or 2,2'-b/s(diphenylphosphino)diphenyl ether.
15. A process according to claim 1 for the preparation of N-(1-methoxyprop-2- yl)-2,6-dimethylphenylamine which comprises allowing (/) 1-methoxy-2-aminopropane and (/'/) 2,6-dimethylphenyl bromide, 2,6-dimethylphenyl chloride, 2,6- dimethylphenyl iodide, 2,6-dimethylphenylmethylsulfonate, or 2,6- dimethylphenyltrifluoromethylsulfonate, to react in a basic environment in the presence of (Hi) palladium(O) or nickel complex catalyst which is palladium chlo- ride, palladium acetate, _b s(frans,fraπs-dibenzylideneacetone)palla- dium, [1 ,1'-b/'s(diphenylphosphino)ferrocene]dichloropalladium, p/s(tri- phenylphosphino)dichloropalladium, tefra/ /s(triphenylphosphine)pal- ladium, b/s(triphenylphosphino)dichloronickel, nickelcarbonyi, or bis- (1 ,5-cyclooctadiene)nickel, and (iv) a ligand which is tri-( ett-butyl)phosphine, 1 ,1'-b/s(diphenylphos- phino)ferrocene, 2,2,-b/s(diphenylphosphino)-1 ,1'-binaphthyl, tri-(o- tolyl)phosphine, 4,12-b/s(diphenylphosphanyl)[2.2]paracyclophane, 1 ,1 '- /s(di-p-methoxyphenylphosphino)ferrocene, 1 ,1 '-b/s(di-p-trifluoro- methylphenylphosphino)ferrocene, 1 , -b s(ditolylphosphino)ferrocene, or 2,2'-b/s(diphenylphosphino)diphenyl ether in which the ratio of palladium(O) complex to ligand is greater than at least 1 :1.
16. The process according to claim 15 wherein the catalytic palladium(O) or nickel complex is b/s(dibenzylideneacetone)palladium or tefra/ds(triphenyl- phosphine)palladium.
17. A process according to claim 1 for the preparation of N-(1-methoxyprop-2- yl)-2-methyl-6-ethylphenylamine which comprises allowing (/) 1 -methoxy-2-aminopropane and (//) 2-methyl-6-ethylphenyl bromide, 2-methyl-6-ethylphenyl chloride, 2-methyl-6-ethylphenyl iodide, 2-methyl-6-ethylphenylmethylsulfonate, or 2-methyl-6-ethylphenyltrifluoromethylsulfonate, to react in a basic environment in the presence of ((Hi) palladium(O) or nickel complex catalyst which is palladium chlo- ride, palladium acetate, b/s(.rat7s, rans-dibenzylideneacetone)palla- dium, [1 ,1'-b/s(diphenylphosphino)ferrocene]dichloropalladium, bis- (triphenylphosphino)dichloropalladium, tefra/ /s(triphenylphosphine)- palladium, b/s(triphenylphosphino)dichloronickel, nickelcarbonyl, or b/s(1 ,5-cyclooctadiene)nickel, and (iv) a ligand which is tri-(tetτ.-butyl)phosphine, 1 ,1'-b/s(diphenylphos- phino)ferrocene, 2,2'-b/s(diphenylphosphino)-1 ,1'-binaphthyl, tri-(o-tol- yl)phosphine, 4,12-b/s(diphenylphosphanyl)[2.2]paracyclophane, 1 ,1'- b/'s(di-p-methoxyphenylphosphino)ferrocene, 1 ,1 '-b/s(di-p-trifluoro- methylphenylphosphino)ferrocene, 1 ,1'-b/s(ditolylphosphino)ferrocene, or 2,2'-b/s(diphenylphosphino)diphenyl ether in which the ratio of palladium(O) complex to ligand is greater than at least 1 :1.
-10-
18. The process according to claim 17 wherein the catalytic palladium(O) or nickel complex is b/s(dibenzylideneacetone)palladium or fefra /s(triphenyi- phosphine)palladium.
19. A process according to claim 17 wherein (S)-1-methoxy-2-aminopropane is employed to yield (S)-N-(1-methoxyprop-2-yl)-2-methyl-6-ethylphenylamine.
-11-
PCT/US2000/026581 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines Ceased WO2001044162A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
NZ519366A NZ519366A (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
IL14980700A IL149807A0 (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
AU77243/00A AU7724300A (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
PCT/US2000/026581 WO2001044162A1 (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
JP2001545251A JP2004507443A (en) 1999-12-14 2000-09-27 Method for preparing secondary and tertiary amines
CA002394519A CA2394519A1 (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
KR1020027007564A KR20020073140A (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
BR0016348-1A BR0016348A (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
HU0203901A HUP0203901A3 (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
EP00966976A EP1237844A1 (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines
MXPA02005810A MXPA02005810A (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines.
FI20020955A FI20020955A7 (en) 1999-12-14 2002-05-21 Method for the preparation of secondary and tertiary amines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60/107,521 1999-12-14
PCT/US2000/026581 WO2001044162A1 (en) 1999-12-14 2000-09-27 Process for the preparation of secondary and tertiary amines

Publications (1)

Publication Number Publication Date
WO2001044162A1 true WO2001044162A1 (en) 2001-06-21

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FI (1) FI20020955A7 (en)
WO (1) WO2001044162A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4757144A (en) * 1983-12-16 1988-07-12 Kao Corporation Preparing tertiary amine from formaldehyde and primary and/or secondary amine
US4792622A (en) * 1985-12-25 1988-12-20 Kao Corporation Process for preparation of secondary amine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4757144A (en) * 1983-12-16 1988-07-12 Kao Corporation Preparing tertiary amine from formaldehyde and primary and/or secondary amine
US4792622A (en) * 1985-12-25 1988-12-20 Kao Corporation Process for preparation of secondary amine

Also Published As

Publication number Publication date
FI20020955L (en) 2002-05-21
FI20020955A7 (en) 2002-06-04

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