EP1794144A2 - Processes for prepating n-(substituted arylmethyl)-4-(disubstituted methyl)piperidines and intermediates - Google Patents

Processes for prepating n-(substituted arylmethyl)-4-(disubstituted methyl)piperidines and intermediates

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Publication number
EP1794144A2
EP1794144A2 EP05798202A EP05798202A EP1794144A2 EP 1794144 A2 EP1794144 A2 EP 1794144A2 EP 05798202 A EP05798202 A EP 05798202A EP 05798202 A EP05798202 A EP 05798202A EP 1794144 A2 EP1794144 A2 EP 1794144A2
Authority
EP
European Patent Office
Prior art keywords
formula
compound
ocf
group
halogen
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.)
Pending
Application number
EP05798202A
Other languages
German (de)
French (fr)
Inventor
Jaidev Goudar
David S. Rosen
Guozhi Wang
Qun Zhang
Russell Patera
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.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
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
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1794144A2 publication Critical patent/EP1794144A2/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Hydrogenated Pyridines (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Improved processes are described for preparing compounds of formulae: (B, C, F, H) wherein R1, R2, B and Z are defined herein. These compounds are useful in the preparation of N-(substituted arylmethyl)-4­(disubstituted methyl)piperidines.

Description

Processes for Preparing N-(Substituted Arylmethyl)-4-(Disubstituted Methyl)Piperidines and Intermediates
This application claims the benefit of U.S. Provisional Application No. 60/609,539, filed September 13, 2004.
Field of the Invention
This invention is in the field of chemical processes; more specifically, processes for preparing intermediates useful in the preparation of N-(substituted arylmethyl)-4-(disubstituted methyl)piperidines.
Backgound
N-(substituted arylmethyl)-4-(disubstituted methyl)piperidines are disclosed in PCT publications 2004/060371 and 2004/060865 as useful insecticides the disclosures of which are incorporated herein by reference. PCT publication 2004/060371 discloses the following general process for synthesizing N-(substituted arylmethyl)-4-(disubstituted methyl)piperidines :
H
i) Mg / 12 / THF /< 40 0C; j) HCl (g) / EtOAc; k) H2 / PtO2 / MeOH; 1) N,N-diisopropylethylamine / DMSO m) Et3N / CH2Cl2 / 35 0C
where R2, R3, R4, R5, and R6 are independently selected from hydrogen, halogen, alkyl, haloalkyl, hydroxyl, alkoxy, haloalkoxy, pentahalothio, alkylthio, cyano, nitro, alkylcarbonyl, alkoxycarbonyl, aryl, or aryloxy, provided that at least one of R2, R3, R4, R5, and R6 are other than hydrogen; and, wherein either of R2 and R3, or R3 and R4 are taken together with -OCF2O-, -OCF2CF2-, -CF2CF2O-, or- CH=CHCH=CH-, forming a benzo-fused ring; R17, R18, R19, R20, and R21 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, cyano, nitro, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylamino, aryl, aryloxy, and 2-alkyl-2H-tetrazole, and, wherein either of R17 and R18, or R18 and R19 may be taken together with -CH2CH=CHCH2-, - OCF2O-, -OCF2CF2-, or -CF2CF2O-, to form benzo-fused rings; and R22, R23, R24, R25, and R26 are independently selected from hydrogen, halogen, alkyl, hydroxy, alkoxy, alkoxyalkyl, dialkoxyalkyl, trialkoxyalkyl, alkoxyiminoalkyl, alkenyloxyiminoalkyl, alkynyloxyiminoalkyl, cycloalkylalkoxy, alkoxyalkoxy, alkylthio, dithioalkoxyalkyl, trithioalkoxyalkyl, alkylsulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, cycloalkylaminosulfonyl, alkenyloxy, alkynyloxy, haloalkenyloxy, alkylsulfonyloxy, optionally substituted arylalkoxy, cyano, nitro, amino, alkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkenyloxycarbonylamino, alkynyloxycarbonylamino, haloalkylcarbonylamino, alkoxyalkoxycarbonylamino, (alkyl)(alkoxycarbonyl)amino, alkylsulfonylamino, optionally substituted (heteroaryl)(alkoxycarbonyl)amino, optionally substituted arylcarbonylamino, foπnyl, optionally substituted l,3-dioxolan-2-yl, optionally substituted l,3-dioxan-2-yl, optionally substituted l,3-oxazolidin-2-yl, optionally substituted l,3-oxazaperhydroin-2-yl, optionally substituted l,3-dithiolan-2-yl, optionally substituted l,3-dithian-2-yl, alkoxycarbonyl, alkylaminocarbonyloxy, alkylaminocarbonylamino, dialkylaminocarbonylamino, alkylamino(thiocarbonyl)amino, dialkylphosphoroureidyl, optionally substituted thienyl, optionally substituted 1,3-thiazolylalkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aryloxyalkyl, optionally substituted arylaminocarbonyloxy, optionally substituted heteroaryl, optionally substituted heteroaryloxy, optionally substituted pyrrolyl, optionally substituted pyrazolyl, optionally substituted pyrazinyloxy. optionally substituted 1,3-oxazolinyl, optionally substituted 1,3-oxazolinyloxy, optionally substituted 1,3- oxazolinylamino, optionally substituted 1,2,4-triazolyl, optionally substituted 1,2,3- thiadiazolyl, optionally substituted 1,2,5-thiadiazolyl, optionally substituted 1,2,5- thiadiazolyloxy, optionally substituted 2H-tetrazolyl, optionally substituted pyridyl, optionally substituted pyridyloxy, optionally substituted pyridylaniino, optionally substituted pyrimidinyl, optionally substituted pyrimidinyloxy, optionally substituted 3,4,5,6-tetrahydropyrimidinyloxy, optionally substituted pyridazinyloxy, or optionally substituted 1,2,3,4-tetrahydronaphthalenyl, wherein the optional substituent is selected from one or more of halogen, alkyl, haloalkyl, alkoxy, dialkoxyalkyl, dithioalkoxyalkyl, cyano, nitro, amino, or alkoxycarbonylamino, provided that at least one of R22, R23, R24, R25, and R26 is other than hydrogen. Disadvantages of this process include less than optimal yields, less than optimal cycle times and high catalyst loadings. Another disadvantage is the highly exothermic first step of the reaction. This significant exothermic reaction is a result of the presence of Mg and fluorine. Marginally controllable, highly exothermic reactions can affect yields and cycle times as well as require costly equipment. The present invention improves yield, cycle times and catalyst loading as well as reduces the exothermic nature of certain of the reactions involved in producing N- (substituted arylmethyl)-4-(disubstituted methyl)piperidines.
Summary of the Invention
The present invention relates to improved processes for preparing intermediates useful in preparing N-(substituted arylmethyl)-4-(disubstituted methyi)piperidines.
Detailed Description of the Invention
In one embodiment the present invention relates to an improved process for preparing a compound of formula B:
B wherein R1 is selected from the group consisting of halogen, CF3, OCF3, OCHF2, OCF2CHF2 and SF5;
said process comprising reacting a substituted aryl halide of formula (A):
Formula (A)
wherein X is halogen; and
R1 is as defined above;
and pyridine-4-carbaldehyde in the presence of an alkyl magnesium halide. The reaction can be conducted in a solvent, preferably tetrahydrofuran, dioxane or monoglyme. Preferably, the alkyl magnesium halide is z-propyl magnesium chloride or /-propyl magnesium bromide.
A second embodiment of the present invention is an improved process for preparing a compound of formula C:
wherein R1 is selected from the group consisting of halogen, CF3, OCF3, OCHF2, OCF2CHF2 and SF5;
said process comprising hydrating a compound of formula B:
B
at elevated pressure.
The hydrating can be conducted with a metal catalyst; in an alcohol solvent. Preferably, the metal catalyst is platinum, palladium or rhodium; the alcohol solvent is methanol or ethanol. Preferably, the elevated pressure is in the range of from 25 pounds per square inch to 200 pounds per square inch. A third embodiment of the present invention is an improved process for preparing a compound of formula F:
wherein
R1 is selected from the group consisting of halogen, CF3, OCF3, OCHF2, OCF2CHF2 and SF5; and
Z and B are independently selected from the group consisting of CH and N;
said process comprising reacting a compound of formula C:
C wherein R1 is as defined above; and a compound selected from the group consisting of i) a compound of formula D:
D wherein Z and B are as defined above;
and ii) a compound of formula E:
E wherein
Y is halogen; and
Z and B are as defined above;
provided that when a compound of formula E is used the reaction is conducted in the presence of a carbonate, a solvent and optionally a phase transfer catalyst.
The reaction can be conducted at a temperature in the range of from ambient temperature to 80°C. The solvent is preferably toluene or methyl isobutyl ketone. The phase transfer catalyst can be polyethylene glycol, dimethylaminopyridine, triethylamine,/?-toluenesulfonic acid, phosphorous pentoxide, pyridine or phase transfer catalysts such as quaternary ammonium salts or quaternary phosphonium salts or mixtures thereof. Preferably, the reaction of a compound of formula C and a compound of formula D is conducted in the presence of a sodium borohydride and a solvent selected from the group consisting of 1,2-dichloroethane, dichloromethane, acetonitrile and tetrahydrofuran.
A fourth embodiment of the present invention is an improved process for preparing a compound of formula H:
H wherein
R1 and R2 are independently selected from the group consisting of halogen, CF3, OCF3, OCHF2, OCF2CHF2 and SF5; and Z and B are independently selected from the group consisting of CH and N;
said process comprising condensing a compound of formula F:
wherein
R1, Z and B are as defined above;
with a compound of formula G:
G
wherein R is as defined above;
in the presence of a solvent selected from the group consisting of 1,2- dichloroethane, acetonitrile and dioxane.
The condensing can be conducted at a temperature in the range of from 40°C to 80°C.
In all embodiments of the present invention: preferably, R1 and R2 are independently selected from the group consisting of halogen, CF3, and OCF3; X is bromine or chlorine; Y is bromine, iodine or chlorine. More preferably, R1 is CF3 and R2 is Cl; X is bromine. Also preferred, Z is N and B is CH.
The modifier "about" is used herein to indicate that certain preferred operating ranges, such as ranges for molar ratios for reactants, material amounts, and temperature, are not fixedly determined. The meaning will often be apparent to one of ordinary skill. For example, a recitation of a temperature range of from about 120° C to about 135° C in reference to, for example, an organic chemical reaction would be interpreted to include other like temperatures that can be expected to favor a useful reaction rate for the reaction, such as 105° C or 150° C. Where guidance from the experience of those of ordinary skill is lacking, guidance from the context is lacking, and where a more specific rule is not recited below, the "about" range shall be not more than 10% of the absolute value of an end point or 10% of the range recited, whichever is less.
As used in this specification and unless otherwise indicated the substituent terms "alkyl", "alkoxy", and "haloalkyl", used alone or as part of a larger moiety, includes straight or branched chains of at least one or two carbon atoms, as appropriate to the substituent, and preferably up to 12 carbon atoms, more preferably up to ten carbon atoms, most preferably up to seven carbon atoms. The term "aryl" refers to phenyl or naphthyl optionally substituted with one or more halogen, alkyl, alkoxy, or haloalkyl. "Halogen", "halide" or "halo" refers to fluorine, bromine, iodine, or chlorine. The term "ambient temperature" refers to a temperature in the range of from about 20° C to about 30° C. Certain solvents, catalysts, and the like are known by their acronyms. These include the acronyms "EDC" meaning 1,2- dichloroethane and "THF" meaning tetrahydrofuran. The term "glymes" refers to a class of solvents comprised of monoglyme, diglyme, triglyme, tetraglyme, and polyglyme.
The following examples illustrate processes of the present invention and an overall process using such processes to prepare N-(substituted arylmethyl)-4- (disubstituted methyl)piperidines of formula (I).
Example 1
Example 1 (cont'd*)
where Z is N where R3 is CHO andB is CH (D)
a) z-PrMgCl/THF/5°C to RT b) H2/25 psi to 35 psi/MeOH c) K2C03/Cu20/145°C to 170°C/12-20 hours e) EDCYNaBH(O Ac)3/35°C to 4O0C/ 3-20 hours f) EDC/35°C to 5O0C/ 2-18 hours g) 80%H2O2/MeOH/40°C to 45°C /9-44 hours In the first step as depicted in Example 1, an appropriately substituted aryl halide, for example, the known compound 4-bromo-l-(trifluoromethyl)benzene (A), and pyridine-4-carbaldehyde were reacted with a Grignard reagent to form the hydrogen chloride salt of 4-pyridyl[4-(trifluoromethyl)phenyl]methan-l-ol (B). Intermediate (B) was then hydrogenated under elevated pressure to afford the corresponding hydrogen chloride salt of 4-piperidyl[4-
(trifluoromethyl)phenyl]methan-l-ol (C). Next, an appropriately substituted phenol, for example, the known compound 4-hydroxybenzaldehyde, was reacted with a halopyridine, for example 2-chloropyridine, in the presence of potassium carbonate and a catalytic amount of copper oxide at a temperature in the range of from 145° C to 170°C to form 4-(2-pyridyloxy)benzaldehyde (D). Intermediate (C) was then reacted with Intermediate (D) in the presence of sodium triacetoxyborohydride at a temperature in the range of from 35 "C to 400C to form {l-[(4-(2- pyridyloxy)phenyl)methyl] (4-piperidyl)} [4-(trifluoromethyl)phenyl]methan- 1 -ol (F). Intermediate (F) was then condensed with an appropriately substituted aryl halide, for example the known compound 4-chlorobenxenisocyanate (G), at a temperature in the range of from 35°C to 50°C to form N-(4-chlorophenyl)({l-[(4- (2-pyridyloxy)phenyl)methyl](4-piperidyi)}[4- (trifluoromethyl)phenyl]methoxy)carboxamide (H). Intermediate (H) was then oxidized with hydrogen peroxide at a temperature in the range of from 40° C to 55°C to forai N-(4-chlorophenyl)({l-oxo-l-[(4-(2-pyridyloxy)phenyl)methyl](4- piperidyl)} [4-(trifluoromethyl)phenyl]methoxy)carboxamide (Formula I).
Example 2
where Z is N where R3 is CH3 andBisCH (D2)
(E)
where R1 is CF,
Example 2 (cont'd)
c) K2CO3/Cu2O/145°C to 170°C/12-20 hours d) Br2 e) K2CO3/toluene /35°C to 4O0C/ 3-20 hours f) EDC/35°C to 500C/ 2-18 hours g) 80%H2O2/MeOH/40°C to 45°C /9-44 hours
In the first step of Example 2, an appropriately substituted phenol, for example, the known compound 4-methyl phenol, can be reacted with a halopyridine, for example 2-chloropyridine, in the presence of potassium carbonate and a catalytic amount of copper oxide at a temperature in the range of from 145°C to 170°C to form 2-(4-methylphenoxy)pyridine (D2). Intermediate (D2) can then be halogenated with, for example bromine, to form 2-[4- (bromomethyl)phenoxy]pyridine (E). Intermediate (C), made as in Example 1, can then be reacted with Intermediate (E) in the presence of potassium carbonate at a temperature in the range of from 35°C to 40°C to form {l-[(4-(2- pyridyloxy)phenyl)methyl] (4-piperidyl) } [4-(trifluoromethyl)phenyl]methan- 1 -ol (F). Intermediate (F) can then be condensed with an appropriately substituted aryl halide, for example the known compound 4-chlorobenxenisocyanate (G), at a temperature in the range of from 35°C to 500C to form N-(4-chlorophenyl)({l-[(4- (2-pyridyloxy)phenyl)methyl](4-piperidyl)}[4-
(trifluoromethyl)phenyl]methoxy)carboxamide (H). Intermediate (H) can then be oxidized with hydrogen peroxide at a temperature in the range of from 40°C to 55°C to form N-(4-chlorophenyiχ { 1 -oxo-1 -[(4-(2-pyridyloxy)phenyl)methyl](4- piperidyl)} [4-(trifluoromethyl)phenyl]methoxy)carboxamide (Formula I). While this invention has been described with an emphasis upon preferred embodiments, it will be obvious to those of ordinary skill in the art that variations of the preferred embodiments may be used and that it is intended that the invention may be practiced otherwise than as specifically described herein. Accordingly this invention includes all modifications encompassed within the spirit and scope as defined by the following claims.

Claims

What is claimed is:
1. A process for preparing a compound of formula B:
B wherein R1 is selected from the group consisting of halogen, CF3, OCF3, OCHF2, OCF2CHF2 and SF5;
said process comprising reacting a substituted aryl halide of formula (A):
Formula (A)
wherein
X is halogen; and
R1 is as defined above;
and pyridine-4-carbaldehyde in the presence of an alkyl magnesium halide.
2. The process of claim 1 wherein R1 is CF3; R2 is Cl; Z is N; and B is CH.
3. The process of claim 1 wherein X is bromine or chlorine.
4. The process of claim 1 wherein the alkyl magnesium halide is z-propyl magnesium chloride or z-propyl magnesium bromide
5. The process of claim 1 wherein the reacting is performed in a solvent.
6. The process of claim 5 wherein the solvent is tetrahydrofuran, dioxane or monoglyme.
7. A process for preparing a compound of formula C :
wherein R1 is selected from the group consisting of halogen, CF3, OCF3, OCHF2, OCF2CHF2 and SF5;
said process comprising hydrating a compound of formula B:
B
at elevated pressure.
8. The process of claim 7 wherein the hydrating is conducted with a metal catalyst in an alcohol solvent.
9. The process of claim 8 wherein the metal catalyst is platinum, palladium or rhodium.
10. The process of claim 8 wherein the alcohol solvent is methanol or ethanol.
11. The process of claim 7 wherein the elevated pressure is in a range of from 25 pounds per square inch to 200 pounds per square inch.
12. A process for preparing a compound of formula F:
wherein
R1 is selected from the group consisting of halogen, CF3, OCF3, OCHF2, OCF2CBDF2 and SF5; and
Z and B are independently selected from the group consisting of CH and N;
said process comprising reacting a compound of formula C:
C wherein R1 is as defined above; and a compound selected from the group consisting of i) a compound of formula D: D wherein Z and B are as defined above;
and ii) a compound of formula E:
wherein
Y is halogen; and
Z and B are as defined above;
provided that when a compound of formula E is used the reaction is conducted in the presence of a carbonate, a solvent and optionally a phase transfer catalyst.
13. The process of claim 12 wherein Y is bromine, iodine or chlorine.
14. The process of claim 12 wherein the reacting of a compound of formula C and a compound of formula D is conducted in the presence of a sodium borohydride and a solvent selected from the group consisting of 1,2- dichloroethane, dichloromethane, acetonitrile and tetrahydrofuran.
15. The process of claim 12 wherein the reacting is conducted at a temperature in the range of from ambient temperature to 80°C.
16. The process of claim 12 wherein the solvent is toluene or methyl isobutyl ketone.
17. The process of claim 12 wherein the phase transfer catalyst is polyethylene glycol.
18. A process for preparing a compound of formula H :
H wherein
R1 and R2 are independently selected from the group consisting of halogen, CF3, OCF3, OCHF2, OCF2CHF2 and SF5; and Z and B are independently selected from the group consisting of CH and N;
said process comprising condensing a compound of formula F:
F wherein
R1, Z and B are as defined above; with a compound of formula G:
wherein R is as defined above;
in the presence of a solvent selected from the group consisting of 1,2- dichloroethane, acetonitrile and dioxane.
19. The process of claim 18 wherein the condensing is conducted at a temperature in the range of from 40°C to 8O0C.
EP05798202A 2004-09-13 2005-09-12 Processes for prepating n-(substituted arylmethyl)-4-(disubstituted methyl)piperidines and intermediates Pending EP1794144A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60953904P 2004-09-13 2004-09-13
PCT/US2005/032473 WO2006031764A2 (en) 2004-09-13 2005-09-12 Processes for prepating n-(substituted arylmethyl)-4-(disubstituted methyl)piperidines and intermediates

Publications (1)

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EP1794144A2 true EP1794144A2 (en) 2007-06-13

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EP (1) EP1794144A2 (en)
JP (1) JP2008512495A (en)
KR (1) KR20070052319A (en)
CN (1) CN101018776A (en)
AR (1) AR052977A1 (en)
BR (1) BRPI0515275A (en)
IL (1) IL181102A0 (en)
TW (1) TW200621747A (en)
WO (1) WO2006031764A2 (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA717147B (en) * 1970-11-27 1972-07-26 Richardson Merrell Inc 4-(4-(alpha-hydroxybenzyl)piperidino)-4'-fluorobutyrophenone derivatives
BR0316747A (en) * 2002-12-18 2005-10-18 Fmc Corp N- (substituted arylmethyl) -4- (disubstituted methyl) piperidines and piperazines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006031764A2 *

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JP2008512495A (en) 2008-04-24
AR052977A1 (en) 2007-04-18
WO2006031764A2 (en) 2006-03-23
WO2006031764A3 (en) 2006-07-13
TW200621747A (en) 2006-07-01
IL181102A0 (en) 2007-07-04
KR20070052319A (en) 2007-05-21
BRPI0515275A (en) 2008-07-15
CN101018776A (en) 2007-08-15

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