Method for preparation of betulinic or betulonic acid from betulin (SE 2011050819)

Jukka Tulisalo, Minni Pirttimaa, Sami Alakurtti, Jari Yli-Kauhaluoma, Salme Koskimies

Forskningsoutput: PatentVetenskaplig

Sammanfattning

The invention relates a method for prepn. of betulonic acid [I; R1 = CO2H] or betulinic acid [II; R2 = CO2H] from betulin [II; R2 = CH2OH] wherein the method comprises a stage for oxidizing II [R2 = CH2OH] to betulonic aldehyde and/or betulinic aldehyde, I [R1 = CHO] and II [R2 = CHO], resp., with Pd(II)-catalyst catalyzed oxidn. process in the presence of dioxygen. Whereby, the Pd(II)-catalyst is LnPd(II)R'R'' [wherein L is an aliph. or heterocyclic ligand contg. at least one nitrogen atom (N-ligand); n is any integer from 0 to 2, in the case n is 0 ligand L is absent; R' or R'' is a functional group selected independently from the group consisting of amines, unsatd. arom. carbocyclic groups, carboxylates, esters, ketones, halogens and nitrate; an unsatd. arom. carbocyclic group have from 6 to 12 carbon atoms 10 and a single ring or multiple condensed (fused) rings, wherein at least one ring is arom. and whereby said unsatd. arom. carbocyclic group may be unsubstituted or substituted; carboxylate means an anion originating from carboxylic acid which forms salt with palladium(II) cation, more preferable carboxylate is originating from a lower carboxylic acid such as acetic acid; ester means an alkyl ester, more preferable lower alkyl ester; and ketone means an alkyl ketone, more preferable lower alkyl ketone or lower alkyl diketone, such as actetylacetonate]. Thus, a mixt. of I [R1 = CO2H] & II [R2 = CO2H] was prepd. from II [R2 = CH2OH] via oxidn. with Pd(OAc)2 in PhMe contg. pyridine followed by N-acetyl-L-cystine (to scavenge Pd) giving betulonic and betulinic aldehydes, I (R1 = CHO) and II (R2 = CHO), resp.; and then, I [R1 = CHO] and II [R2 = CHO] were oxidized with NaClO2 in t-BuOH contg. 2-methyl-2-butene and aq. NaH2PO4·H2O.
Originalspråksvenska
Utgivningsår13 mar 2013
StatusPublicerad - 13 mar 2013
MoE-publikationstypH1 Beviljat patent

Citera det här

Tulisalo, J., Pirttimaa, M., Alakurtti, S., Yli-Kauhaluoma, J., & Koskimies, S. (2013). Method for preparation of betulinic or betulonic acid from betulin (SE 2011050819). (Patentnr. SE 2011050819).
Tulisalo, Jukka (Författare) ; Pirttimaa, Minni (Författare) ; Alakurtti, Sami (Författare) ; Yli-Kauhaluoma, Jari (Författare) ; Koskimies, Salme (Författare). / Method for preparation of betulinic or betulonic acid from betulin (SE 2011050819). Patentnr.: SE 2011050819. mar 13, 2013.
@misc{9db7bd9b0d324b2db6a4046ff199199c,
title = "Method for preparation of betulinic or betulonic acid from betulin (SE 2011050819)",
abstract = "The invention relates a method for prepn. of betulonic acid [I; R1 = CO2H] or betulinic acid [II; R2 = CO2H] from betulin [II; R2 = CH2OH] wherein the method comprises a stage for oxidizing II [R2 = CH2OH] to betulonic aldehyde and/or betulinic aldehyde, I [R1 = CHO] and II [R2 = CHO], resp., with Pd(II)-catalyst catalyzed oxidn. process in the presence of dioxygen. Whereby, the Pd(II)-catalyst is LnPd(II)R'R'' [wherein L is an aliph. or heterocyclic ligand contg. at least one nitrogen atom (N-ligand); n is any integer from 0 to 2, in the case n is 0 ligand L is absent; R' or R'' is a functional group selected independently from the group consisting of amines, unsatd. arom. carbocyclic groups, carboxylates, esters, ketones, halogens and nitrate; an unsatd. arom. carbocyclic group have from 6 to 12 carbon atoms 10 and a single ring or multiple condensed (fused) rings, wherein at least one ring is arom. and whereby said unsatd. arom. carbocyclic group may be unsubstituted or substituted; carboxylate means an anion originating from carboxylic acid which forms salt with palladium(II) cation, more preferable carboxylate is originating from a lower carboxylic acid such as acetic acid; ester means an alkyl ester, more preferable lower alkyl ester; and ketone means an alkyl ketone, more preferable lower alkyl ketone or lower alkyl diketone, such as actetylacetonate]. Thus, a mixt. of I [R1 = CO2H] & II [R2 = CO2H] was prepd. from II [R2 = CH2OH] via oxidn. with Pd(OAc)2 in PhMe contg. pyridine followed by N-acetyl-L-cystine (to scavenge Pd) giving betulonic and betulinic aldehydes, I (R1 = CHO) and II (R2 = CHO), resp.; and then, I [R1 = CHO] and II [R2 = CHO] were oxidized with NaClO2 in t-BuOH contg. 2-methyl-2-butene and aq. NaH2PO4·H2O.",
author = "Jukka Tulisalo and Minni Pirttimaa and Sami Alakurtti and Jari Yli-Kauhaluoma and Salme Koskimies",
year = "2013",
month = "3",
day = "13",
language = "svenska",
type = "Patent",
note = "SE 2011050819",

}

Tulisalo, J, Pirttimaa, M, Alakurtti, S, Yli-Kauhaluoma, J & Koskimies, S mar. 13 2013, Method for preparation of betulinic or betulonic acid from betulin (SE 2011050819), Patentnr. SE 2011050819.

Method for preparation of betulinic or betulonic acid from betulin (SE 2011050819). / Tulisalo, Jukka; Pirttimaa, Minni; Alakurtti, Sami; Yli-Kauhaluoma, Jari; Koskimies, Salme.

Patentnr.: SE 2011050819. mar 13, 2013.

Forskningsoutput: PatentVetenskaplig

TY - PAT

T1 - Method for preparation of betulinic or betulonic acid from betulin (SE 2011050819)

AU - Tulisalo, Jukka

AU - Pirttimaa, Minni

AU - Alakurtti, Sami

AU - Yli-Kauhaluoma, Jari

AU - Koskimies, Salme

PY - 2013/3/13

Y1 - 2013/3/13

N2 - The invention relates a method for prepn. of betulonic acid [I; R1 = CO2H] or betulinic acid [II; R2 = CO2H] from betulin [II; R2 = CH2OH] wherein the method comprises a stage for oxidizing II [R2 = CH2OH] to betulonic aldehyde and/or betulinic aldehyde, I [R1 = CHO] and II [R2 = CHO], resp., with Pd(II)-catalyst catalyzed oxidn. process in the presence of dioxygen. Whereby, the Pd(II)-catalyst is LnPd(II)R'R'' [wherein L is an aliph. or heterocyclic ligand contg. at least one nitrogen atom (N-ligand); n is any integer from 0 to 2, in the case n is 0 ligand L is absent; R' or R'' is a functional group selected independently from the group consisting of amines, unsatd. arom. carbocyclic groups, carboxylates, esters, ketones, halogens and nitrate; an unsatd. arom. carbocyclic group have from 6 to 12 carbon atoms 10 and a single ring or multiple condensed (fused) rings, wherein at least one ring is arom. and whereby said unsatd. arom. carbocyclic group may be unsubstituted or substituted; carboxylate means an anion originating from carboxylic acid which forms salt with palladium(II) cation, more preferable carboxylate is originating from a lower carboxylic acid such as acetic acid; ester means an alkyl ester, more preferable lower alkyl ester; and ketone means an alkyl ketone, more preferable lower alkyl ketone or lower alkyl diketone, such as actetylacetonate]. Thus, a mixt. of I [R1 = CO2H] & II [R2 = CO2H] was prepd. from II [R2 = CH2OH] via oxidn. with Pd(OAc)2 in PhMe contg. pyridine followed by N-acetyl-L-cystine (to scavenge Pd) giving betulonic and betulinic aldehydes, I (R1 = CHO) and II (R2 = CHO), resp.; and then, I [R1 = CHO] and II [R2 = CHO] were oxidized with NaClO2 in t-BuOH contg. 2-methyl-2-butene and aq. NaH2PO4·H2O.

AB - The invention relates a method for prepn. of betulonic acid [I; R1 = CO2H] or betulinic acid [II; R2 = CO2H] from betulin [II; R2 = CH2OH] wherein the method comprises a stage for oxidizing II [R2 = CH2OH] to betulonic aldehyde and/or betulinic aldehyde, I [R1 = CHO] and II [R2 = CHO], resp., with Pd(II)-catalyst catalyzed oxidn. process in the presence of dioxygen. Whereby, the Pd(II)-catalyst is LnPd(II)R'R'' [wherein L is an aliph. or heterocyclic ligand contg. at least one nitrogen atom (N-ligand); n is any integer from 0 to 2, in the case n is 0 ligand L is absent; R' or R'' is a functional group selected independently from the group consisting of amines, unsatd. arom. carbocyclic groups, carboxylates, esters, ketones, halogens and nitrate; an unsatd. arom. carbocyclic group have from 6 to 12 carbon atoms 10 and a single ring or multiple condensed (fused) rings, wherein at least one ring is arom. and whereby said unsatd. arom. carbocyclic group may be unsubstituted or substituted; carboxylate means an anion originating from carboxylic acid which forms salt with palladium(II) cation, more preferable carboxylate is originating from a lower carboxylic acid such as acetic acid; ester means an alkyl ester, more preferable lower alkyl ester; and ketone means an alkyl ketone, more preferable lower alkyl ketone or lower alkyl diketone, such as actetylacetonate]. Thus, a mixt. of I [R1 = CO2H] & II [R2 = CO2H] was prepd. from II [R2 = CH2OH] via oxidn. with Pd(OAc)2 in PhMe contg. pyridine followed by N-acetyl-L-cystine (to scavenge Pd) giving betulonic and betulinic aldehydes, I (R1 = CHO) and II (R2 = CHO), resp.; and then, I [R1 = CHO] and II [R2 = CHO] were oxidized with NaClO2 in t-BuOH contg. 2-methyl-2-butene and aq. NaH2PO4·H2O.

M3 - Patent

M1 - SE 2011050819

Y2 - 2013/03/13

ER -

Tulisalo J, Pirttimaa M, Alakurtti S, Yli-Kauhaluoma J, Koskimies S. Method for preparation of betulinic or betulonic acid from betulin (SE 2011050819). SE 2011050819. 2013 mar 13.