US4308376A
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Synthesis of 2-amino-2-deoxyglycoses and 2-amino-2-deoxyglycosides from glycals
Assignee: Alberta Innovates
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Filing: 1979-09-19
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Granted: 1981-12-29
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Expires: 1999-09-19
Abstract
Abstract O-acetylated glycals react with ceric ammonium nitrate in the presence of sodium azide to provide, in good yield, O-acetylated 2-azido-2-deoxy glycosyl nitrates. These nitrates can be used to prepare 2-amino-2-deoxy sugars, such as D-galactosamine and lactosamine. The O-acetylated 2-azido-2-deoxy glycosyl nitrates can alternately be converted to O-acetylated 2-azido-2-deoxy glycosyl halides which are useful in the preparation of O-acetylated 2-azido-2-deoxy glycosides, which in turn can be reduced to 2-amino-2-deoxy glycosides. Of particular interest are the syntheses of 2-amino-2-deoxy glycosides which correspond to the terminal units of the antigenic determinant for the human A blood group. Attachment of these glycosides to a solid support provides immunoabsorbents which efficiently and preferentially absorb anti-A antibodies from blood plasma.
Inventors
- 👤 Raymond U. Lemieux
- 👤 R. Murray Ratcliffe
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 10:31
CPC Classifications
C; C07; C07H; C07H5/00; C07H5/04; C07H5/06; A; A61; A61P; A61P37/00; C07H13/00; C07H13/02; C07H13/08; C07H15/00; C07H15/02; C07H15/04; C07H3/00; C07H3/06
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
55 words
A process which comprises: reacting an acylated glycal with ceric ammonium nitrate and an azide salt in a suitable solvent with stirring to form acylated 2-azido-2-deoxy glycosyl nitrate; and converting the acylated 2-azido-2-deoxy glycosyl nitrate to a 2-amino-2-deoxy glycose by reducing the azido group to an amino group and hydrolyzing the acyl and nitrate groups.
Claim 2
Dependent Claim
55 words
A process which comprises: reacting an acylated glycal with ceric ammonium nitrate and an azide salt in a suitable solvent with stirring to form acylated 2-azido-2-deoxy glycosyl nitrate; and converting the acylated 2-azido-2-deoxy glycosyl nitrate to a 2-amino-2-deoxy glycose by reducing the azido group to an amino group and hydrolyzing the acyl and nitrate groups.
Claim 3
Dependent Claim
23 words
The process of claim 1 wherein the reduction of the azide group comprises reacting said nitrate with acetic acid over finely-divided zinc metal.
Claim 4
Dependent Claim
29 words
The process of claim 1 wherein the reduction of the azide group comprises hydrogenating said nitrate over a catalyst, wherein the catalyst is one of palladium, platinum and nickel.
Claim 5
Dependent Claim
61 words
A process which comprises: reacting an acylated glycal with ceric ammonium nitrate and an azide salt in a suitable solvent with stirring to form acylated 2-azido-2-deoxy glycosyl nitrate; and reducing the azido group of the acylated 2-azido-2-deoxy glycosyl nitrate to an amine and treating said reduction product with an aqueous mineral acid to produce the acid salt of the 2-amino-2-deoxy glycose.
Claim 6
Dependent Claim
61 words
A process which comprises: reacting an acylated glycal with ceric ammonium nitrate and an azide salt in a suitable solvent with stirring to form acylated 2-azido-2-deoxy glycosyl nitrate; and reducing the azido group of the acylated 2-azido-2-deoxy glycosyl nitrate to an amine and treating said reduction product with an aqueous mineral acid to produce the acid salt of the 2-amino-2-deoxy glycose.
Claim 7
Dependent Claim
13 words
The process of claim 4 wherein the aqueous mineral acid is hydrochloric acid.
Claim 8
Dependent Claim
39 words
A process which comprises displacing the nitrate group of an acylated 2-azido-2-deoxy glycosyl nitrate with an acyl group, reducing the azido group to amine and hydrolyzing with an aqueous mineral acid to produce the salt of the 2-amino-2-deoxy glycose.
Claim 9
Dependent Claim
39 words
A process which comprises displacing the nitrate group of an acylated 2-azido-2-deoxy glycosyl nitrate with an acyl group, reducing the azido group to amine and hydrolyzing with an aqueous mineral acid to produce the salt of the 2-amino-2-deoxy glycose.
Claim 10
Dependent Claim
19 words
The process of claim 6 wherein the acyl group is acetyl and the aqueous mineral acid is hydrochloric acid.
Claim 11
Dependent Claim
32 words
A process which comprises displacing the nitrate group of an acylated 2-azido-2-deoxy glycosyl nitrate with an acyl group, hydrolyzing the product and reducing the azido group of the hydrolyzed product to amine.
Claim 12
Dependent Claim
32 words
A process which comprises displacing the nitrate group of an acylated 2-azido-2-deoxy glycosyl nitrate with an acyl group, hydrolyzing the product and reducing the azido group of the hydrolyzed product to amine.
Claim 13
Dependent Claim
63 words
The process of claim 6 wherein: displacement of the nitrate group by an acetate is effected by dissolving an anomeric mixture of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl nitrate in a solution of sodium acetate in acetic acid and heating the solution; and reduction of the azido group to amine is effected by adding zinc dust and acetic anhydride with stirring to provide an anomeric mixture of 2-acetamido-1,3,4,6-tetra-O-acetyl-D-galactopyranose.
Claim 14
Dependent Claim
30 words
The process of claim 9 which includes isolating the product by solvent extraction after the addition of water, and treating said product with aqueous hydrochloric acid to form D-galactosamine hydrochloride.
Claim 15
Dependent Claim
13 words
The process of claim 10 which includes isolating D-galactosamine by evaporation under vacuum.
Claim 16
Dependent Claim
57 words
The process which comprises reacting an anomeric mixture of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl nitrate with sodium acetate in acetic acid to form the 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl acetates, isolating said product, hydrolyzing said isolated product in an aqueous acid to provide 2-azido-2-deoxy-D-galactose, and reducing the 2-azido-2-deoxy-D-galactose in the presence of a molar equivalent of acid to produce the corresponding acid salt of D-galactosamine.
Claim 17
Dependent Claim
57 words
The process which comprises reacting an anomeric mixture of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl nitrate with sodium acetate in acetic acid to form the 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl acetates, isolating said product, hydrolyzing said isolated product in an aqueous acid to provide 2-azido-2-deoxy-D-galactose, and reducing the 2-azido-2-deoxy-D-galactose in the presence of a molar equivalent of acid to produce the corresponding acid salt of D-galactosamine.
Claim 18
Dependent Claim
49 words
The process which comprises reacting an anomeric mixture of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl nitrate with sodium acetate in acetic acid to form the 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl acetates, isolating said product, hydrolyzing said isolated product in an aqueous acid to provide 2-azido-2-deoxy-D-galactose, and reducing the 2-azido-2-deoxy-D-galactose and then N-acetylating the D-galactosamine product to form N-acetyl-D-galactosamine.
Claim 19
Dependent Claim
49 words
The process which comprises reacting an anomeric mixture of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl nitrate with sodium acetate in acetic acid to form the 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl acetates, isolating said product, hydrolyzing said isolated product in an aqueous acid to provide 2-azido-2-deoxy-D-galactose, and reducing the 2-azido-2-deoxy-D-galactose and then N-acetylating the D-galactosamine product to form N-acetyl-D-galactosamine.
Claim 20
Dependent Claim
18 words
The process of claim 6 wherein: the acylated 2-azido-2-deoxy glycosyl nitrate is an anomeric mixture of 3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-azido-2-deoxy-D-glucopyranosyl nitrate.
Claim 21
Dependent Claim
32 words
The process which comprises reacting an anomeric mixture of 3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-azido-2-deoxy-D-glucopyranosyl nitrate with sodium acetate in acetic acid to replace the nitrate, reducing the azide, acetylating the product and de-O-acetylating to form N-acetyllactosamine.
Claim 22
Dependent Claim
32 words
The process which comprises reacting an anomeric mixture of 3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-azido-2-deoxy-D-glucopyranosyl nitrate with sodium acetate in acetic acid to replace the nitrate, reducing the azide, acetylating the product and de-O-acetylating to form N-acetyllactosamine.
Claim 23
Dependent Claim
44 words
A process for preparing 2-acetamido-2-deoxy glycoses from acylated-2-azido-2-deoxy glycosyl nitrates comprising: displacing the nitrate group of the acylated-2-azido-2-deoxy glycosyl nitrate with an acyl group; reducing the azido group to an amine; and acetylating the amine to an acetamido group to produce a 2-acetamido-2-deoxy glycose.
Claim 24
Dependent Claim
44 words
A process for preparing 2-acetamido-2-deoxy glycoses from acylated-2-azido-2-deoxy glycosyl nitrates comprising: displacing the nitrate group of the acylated-2-azido-2-deoxy glycosyl nitrate with an acyl group; reducing the azido group to an amine; and acetylating the amine to an acetamido group to produce a 2-acetamido-2-deoxy glycose.
References Cited (Backward Citations)
US2094693A
Cited
US3496196A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-12-28 | 1985-06-29 | 1985-12-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-12-28 | 1989-06-29 | 1989-12-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-12-28 | 1993-06-29 | 1993-12-29 | $7700.00 | Window Closed / Lapsed |