Patent US4181795A successfully refreshed from Google Patents.
US4181795A
Expired / Lapsed
US
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Daunosamine synthesis
Assignee: Purdue Research Foundation
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Filing: 1978-05-22
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Granted: 1980-01-01
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Expires: 1998-05-22
Abstract
Abstract A process for synthesizing daunosamine and related compounds is disclosed. Intermediates useful for synthesizing daunosamine, and processes for preparing such intermediates, are also disclosed.
Inventors
- 👤 Roy L. Whistler
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 01:18
CPC Classifications
C; C07; C07H; C07H5/00; C07H5/04; C07H5/06; C07H13/00; C07H13/02; C07H13/04; C07H9/00; C07H9/02; C07H9/04
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
204 words
A process for making methyl 3-substituted amino-2,3,6,-trideoxy-β-L-lyxo-hexopyranoside comprising: (a) reacting 1,2:5,6-di-O-isopropylidene-3-amino-3-deoxy-α-D-allofuranose with a compound containing a blocking group whereby a blocking group is introduced on the amino group; (b) reacting the resultant 1,2:5,6-di-O-isopropylidene-3-substituted amino-3-deoxy-α-D-allofuranose with a weak acid to produce 1,2-O-isopropylidene-3-substituted amino-3-deoxy-α-D-allofuranose; (c) subjecting the resultant 1,2-O-isopropylidene-3-substituted amino-3-deoxy-α-D-allofuranose to benzoylation and tosylation to produce 1,2-O-isopropylidene-3-substituted amino-6-O-benzoyl-5-O-tolylsulfonyl-3-deoxy-α-D-allofuranose; (d) removing the benzoate group, and the toluene sulfonate group from the resultant 1,2-O-isopropylidene-3-substituted amino-6-O-benzoyl-5-O-tolysulfonyl-3-deoxy-α-D-allofuranose by condensing them in a low molecular weight alcohol, under basic conditions, to produce 1,2-O-isopropylidene-3-substituted amino-5,6-anhydro-3-deoxy-β-L-talofuranose; (e) reducing 1,2,-O-isopropylidene-3-substituted amino-5,6-anhydro-3-dideoxy-β-L-talofuranose to produce 1,2,-O-isopropylidene-3-substituted amino-3,6-deoxy-β-L-talofuranose; (f) reacting the resultant 1,2-O-isopropylidene-3-substituted amino-3,6-dideoxy-β-L-talofuranose with a strong acid and reacting the resultant product with a compound containing a blocking group, whereby a blocking group containing product is formed corresponding to the formula ##STR28## wherein R is a blocking group: (g) halogenating the resultant blocking group containing product to produce a halogenated derivative corresponding to the formula ##STR29## wherein R is a blocking group and X is halogen; (h) reducing the resultant chlorinated or brominated derivative to form a glycal having the formula ##STR30## wherein R is said blocking group; and (i) subjecting said glycal to methoxymercuration and reducing the resultant product whereby methyl 3-substituted amino-2,3,6,-trideoxy-β-L-lyxo-hexopyranoside is formed.
Claim 2
Dependent Claim
204 words
A process for making methyl 3-substituted amino-2,3,6,-trideoxy-β-L-lyxo-hexopyranoside comprising: (a) reacting 1,2:5,6-di-O-isopropylidene-3-amino-3-deoxy-α-D-allofuranose with a compound containing a blocking group whereby a blocking group is introduced on the amino group; (b) reacting the resultant 1,2:5,6-di-O-isopropylidene-3-substituted amino-3-deoxy-α-D-allofuranose with a weak acid to produce 1,2-O-isopropylidene-3-substituted amino-3-deoxy-α-D-allofuranose; (c) subjecting the resultant 1,2-O-isopropylidene-3-substituted amino-3-deoxy-α-D-allofuranose to benzoylation and tosylation to produce 1,2-O-isopropylidene-3-substituted amino-6-O-benzoyl-5-O-tolylsulfonyl-3-deoxy-α-D-allofuranose; (d) removing the benzoate group, and the toluene sulfonate group from the resultant 1,2-O-isopropylidene-3-substituted amino-6-O-benzoyl-5-O-tolysulfonyl-3-deoxy-α-D-allofuranose by condensing them in a low molecular weight alcohol, under basic conditions, to produce 1,2-O-isopropylidene-3-substituted amino-5,6-anhydro-3-deoxy-β-L-talofuranose; (e) reducing 1,2,-O-isopropylidene-3-substituted amino-5,6-anhydro-3-dideoxy-β-L-talofuranose to produce 1,2,-O-isopropylidene-3-substituted amino-3,6-deoxy-β-L-talofuranose; (f) reacting the resultant 1,2-O-isopropylidene-3-substituted amino-3,6-dideoxy-β-L-talofuranose with a strong acid and reacting the resultant product with a compound containing a blocking group, whereby a blocking group containing product is formed corresponding to the formula ##STR28## wherein R is a blocking group: (g) halogenating the resultant blocking group containing product to produce a halogenated derivative corresponding to the formula ##STR29## wherein R is a blocking group and X is halogen; (h) reducing the resultant chlorinated or brominated derivative to form a glycal having the formula ##STR30## wherein R is said blocking group; and (i) subjecting said glycal to methoxymercuration and reducing the resultant product whereby methyl 3-substituted amino-2,3,6,-trideoxy-β-L-lyxo-hexopyranoside is formed.
Claim 3
Dependent Claim
41 words
The process of claim 1 where the 1,2:5,6-di-O-isopropylidene-3-amino-3-deoxy-α-D-allofuranose is prepared by reacting D-glucose with acetone to produce 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose, oxidizing the glucofuranose to produce 1,2:5,6-di-O-isopropylidene-α-D-ribo-hexofuranose-3-ulose, subjecting the hexofuranose to oximization to produce 1,2:5,6-di-O-isopropylidene-α-D-ribo-hexofuranose-3-ulose oxime, and reducing the oxime to produce said 1,2:5,6-di-O-isopropylidene-3-amino-3-deoxy-α-D-allofuranose.
Claim 4
Dependent Claim
21 words
The process of claim 1 wherein said methyl-3-substituted amino-2,3,6-trideoxy-β-L-lyxo-hexopyranoside is converted to daunosamine hydrochloride by reacting said hexopyranoside with hydrochloric acid.
Claim 5
Dependent Claim
49 words
The process of claim 1 wherein said methyl 3-substituted amino-2,3,6-trideoxy-β-L-lyxo-hexopyranoside is converted to a compound having the formula: ##STR31## by reacting said hexopyranoside with a reagent selected from the group consisting of (1) RX or (2) HX and ROH, wherein R is ##STR32## and X is Cl or Br.
Claim 6
Dependent Claim
16 words
A process for producing 1,2:5,6-di-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose comprising reacting 1,2:5,6-di-O-isopropylidene-3-amino-3-deoxy-α-D-allofuranose with trifluoroacetic anhydride whereby said 1,2:5,6-di-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose is formed.
Claim 7
Dependent Claim
16 words
A process for producing 1,2:5,6-di-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose comprising reacting 1,2:5,6-di-O-isopropylidene-3-amino-3-deoxy-α-D-allofuranose with trifluoroacetic anhydride whereby said 1,2:5,6-di-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose is formed.
Claim 8
Dependent Claim
16 words
A process for producing 1,2-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose comprising reacting 1,2:5,6-di-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose with acetic acid whereby said 1,2-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose is formed.
Claim 9
Dependent Claim
16 words
A process for producing 1,2-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose comprising reacting 1,2:5,6-di-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose with acetic acid whereby said 1,2-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose is formed.
Claim 10
Dependent Claim
19 words
A process for producing 1,2-O-isopropylidene-3-trifluoroacetamido-6-O-benzoyl-5-O-tolylsulfonyl-3-deoxy-α-D-allofuranose which comprises reacting 1,2-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose with benzoyl chloride and tolylsulfonyl chloride whereby 1,2-O-isopropylidene-3-trifluoroacetamido-6-O-benzoyl-5-O-tolylsulfonyl-3-deoxy-α-D-allofuranose is formed.
Claim 11
Dependent Claim
19 words
A process for producing 1,2-O-isopropylidene-3-trifluoroacetamido-6-O-benzoyl-5-O-tolylsulfonyl-3-deoxy-α-D-allofuranose which comprises reacting 1,2-O-isopropylidene-3-trifluoroacetamido-3-deoxy-α-D-allofuranose with benzoyl chloride and tolylsulfonyl chloride whereby 1,2-O-isopropylidene-3-trifluoroacetamido-6-O-benzoyl-5-O-tolylsulfonyl-3-deoxy-α-D-allofuranose is formed.
Claim 12
Dependent Claim
22 words
A process for producing 1,2-O-isopropylidene-3-trifluoroacetamido-5,6-anhydro-3-deoxy-β-L-talofuranose which comprises reacting 1,2-O-isopropylidene-3-trifluoroacetamido-6-O-benzoyl-5-O-tolylsulfonyl-3-deoxy-α-D-allofuranose with a solution of sodium methoxide in methyl alcohol whereby 1,2-O-isopropylidene-3-trifluoroacetamido-5,6-anhydro-3-deoxy-β-L-talofuranose is produced.
Claim 13
Dependent Claim
22 words
A process for producing 1,2-O-isopropylidene-3-trifluoroacetamido-5,6-anhydro-3-deoxy-β-L-talofuranose which comprises reacting 1,2-O-isopropylidene-3-trifluoroacetamido-6-O-benzoyl-5-O-tolylsulfonyl-3-deoxy-α-D-allofuranose with a solution of sodium methoxide in methyl alcohol whereby 1,2-O-isopropylidene-3-trifluoroacetamido-5,6-anhydro-3-deoxy-β-L-talofuranose is produced.
Claim 14
Dependent Claim
17 words
A process for producing 1,2-O-isopropylidene-3-trifluoracetamido-3,6-dideoxy-β-L-talofuranose comprising reducing 1,2-O-isopropylidene-3-trifluoroacetamido-5,6-anhydro-3-deoxy-β-L-talofuranose with a metallic catalyst whereby said 1,2-O-isopropylidene-3-trifluoroacetamido-3,6-dideoxy-β-L-talofuranose is produced.
Claim 15
Dependent Claim
17 words
A process for producing 1,2-O-isopropylidene-3-trifluoracetamido-3,6-dideoxy-β-L-talofuranose comprising reducing 1,2-O-isopropylidene-3-trifluoroacetamido-5,6-anhydro-3-deoxy-β-L-talofuranose with a metallic catalyst whereby said 1,2-O-isopropylidene-3-trifluoroacetamido-3,6-dideoxy-β-L-talofuranose is produced.
Claim 16
Dependent Claim
19 words
A process for producing 3-trifluoroacetamido-1,2,4-tri-O-acetyl-3,6-dideoxy-β-L-talopyranose comprising reacting 1,2-O-isopropylidene-3-trifluoroacetamido-3,6-dideoxy-β-L-talofuranose with sulfuric acid and acetic anhydride, where said 3-trifluoroacetamido-1,2,4-tri-O-acetyl-3,6-dideoxy-β-L-talopyranose is produced.
Claim 17
Dependent Claim
19 words
A process for producing 3-trifluoroacetamido-1,2,4-tri-O-acetyl-3,6-dideoxy-β-L-talopyranose comprising reacting 1,2-O-isopropylidene-3-trifluoroacetamido-3,6-dideoxy-β-L-talofuranose with sulfuric acid and acetic anhydride, where said 3-trifluoroacetamido-1,2,4-tri-O-acetyl-3,6-dideoxy-β-L-talopyranose is produced.
Claim 18
Dependent Claim
18 words
A process for producing 3-trifluoroacetamido-2,4-di-O-acetyl-3,6-dideoxy-β-L-talopyranosyl bromide comprising reacting 3-trifluoroacetamido-1,2,4-tri-O-acetyl-3,6-dideoxy-β-L-talopyranose with hydrogen bromide whereby said 3-trifluoroacetamido-2,4-di-O-acetyl-3,6-dideoxy-β-L-talopyranosyl bromide is formed.
Claim 19
Dependent Claim
18 words
A process for producing 3-trifluoroacetamido-2,4-di-O-acetyl-3,6-dideoxy-β-L-talopyranosyl bromide comprising reacting 3-trifluoroacetamido-1,2,4-tri-O-acetyl-3,6-dideoxy-β-L-talopyranose with hydrogen bromide whereby said 3-trifluoroacetamido-2,4-di-O-acetyl-3,6-dideoxy-β-L-talopyranosyl bromide is formed.
Claim 20
Dependent Claim
14 words
A process for producing 3-trifluoroacetamido-4-O-acetyl-1,2,3,6-tetradeoxy-L-lyxo-hex-1-enepyranose comprising reducing 3-trifluoroacetamido-2,4-di-O-acetyl-3,6-dideoxy-β-L-talopyranosyl bromide whereby said 3-trifluoroacetamido-4-O-acetyl-1,2,3,6-tetradeoxy-L-lyxo-hex-1-enepyranose is formed.
Claim 21
Dependent Claim
14 words
A process for producing 3-trifluoroacetamido-4-O-acetyl-1,2,3,6-tetradeoxy-L-lyxo-hex-1-enepyranose comprising reducing 3-trifluoroacetamido-2,4-di-O-acetyl-3,6-dideoxy-β-L-talopyranosyl bromide whereby said 3-trifluoroacetamido-4-O-acetyl-1,2,3,6-tetradeoxy-L-lyxo-hex-1-enepyranose is formed.
Claim 22
Dependent Claim
20 words
A process for making methyl-3-trifluoroacetamido-2,3,6-trideoxy-β-L-lyxo-hexopyranoside comprising reacting 3-trifluoroacetamido-4-O-acetyl-1,2,3,6-tetradeoxy-L-lyxo-hex-1-enepyranose with mercuric acetate and reducing the resultant product whereby methyl-3-trifluoroacetamido-2,3,6-trideoxy-β-L-lyxo-hexopyranoside is formed.
Claim 23
Dependent Claim
20 words
A process for making methyl-3-trifluoroacetamido-2,3,6-trideoxy-β-L-lyxo-hexopyranoside comprising reacting 3-trifluoroacetamido-4-O-acetyl-1,2,3,6-tetradeoxy-L-lyxo-hex-1-enepyranose with mercuric acetate and reducing the resultant product whereby methyl-3-trifluoroacetamido-2,3,6-trideoxy-β-L-lyxo-hexopyranoside is formed.
Claim 24
Dependent Claim
106 words
A compound having the formula ##STR33## wherein R is H, ##STR34## R 1 is H, HO-, CH 3 C 6 H 4 SO 2 O--; or CH 3 SO 2 O--; R 2 is H, --OH, or, in combination with R 4 , >O; R 3 is H, HO--, or ##STR35## and R 4 is H or, in combination with R 2 , >O; provided that one of R 1 or R 2 and one of R 3 or R 4 must be H, and at least one of R 1 , R 2 , R 3 , and R 4 must be other than H.
Claim 25
Dependent Claim
106 words
A compound having the formula ##STR33## wherein R is H, ##STR34## R 1 is H, HO-, CH 3 C 6 H 4 SO 2 O--; or CH 3 SO 2 O--; R 2 is H, --OH, or, in combination with R 4 , >O; R 3 is H, HO--, or ##STR35## and R 4 is H or, in combination with R 2 , >O; provided that one of R 1 or R 2 and one of R 3 or R 4 must be H, and at least one of R 1 , R 2 , R 3 , and R 4 must be other than H.
Claim 26
Dependent Claim
24 words
The compound of claim 14 where R is ##STR36## R 1 and R 3 are HO--, and R 2 and R 4 are H.
Claim 27
Dependent Claim
33 words
The compound of claim 14 where R is ##STR37## R 1 is CH 3 C 6 H 4 SO 2 O--, R 3 is ##STR38## and R 2 and R 4 are H.
Claim 28
Dependent Claim
19 words
The compound of claim 14 where R is H and R 2 and R 4 are, in combination, >O.
Claim 29
Dependent Claim
23 words
The compound of claim 14 where R, R 1 , R 3 , and R 4 are H, and R 2 is --OH.
Claim 30
Dependent Claim
34 words
A compound of the formula ##STR39## wherein R and R 1 , which may be the same or different, are ##STR40## R 2 is ##STR41## ; and R 3 is ##STR42## Cl--, or Br--.
Claim 31
Dependent Claim
34 words
A compound of the formula ##STR39## wherein R and R 1 , which may be the same or different, are ##STR40## R 2 is ##STR41## ; and R 3 is ##STR42## Cl--, or Br--.
Claim 32
Dependent Claim
21 words
The compound of claim 19 where R and R 1 , are ##STR43## and R 2 and R 3 are ##STR44##
Claim 33
Dependent Claim
20 words
The compound of claim 19 where R and R 1 are R 2 is ##STR45## and R 3 is Br.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-12-31 | 1983-07-02 | 1984-01-01 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-12-31 | 1987-07-02 | 1988-01-01 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-12-31 | 1991-07-02 | 1992-01-01 | $7700.00 | Window Closed / Lapsed |