# US 5,708,152 A · N-substituted chitosan derivatives in a process for their preparation

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- Number: US 5,708,152 A
- Document ID: US5708152A
- Status: Granted
- Kind: A
- Application number: 08/451,324
- Filed: 1995-05-26
- Granted: 1998-01-13
- Earliest claimed: 1992-03-27
- Assignees: Ciba Specialty Chemicals Corporation
- Inventors: Dieter Lohmann; Donald Richard Randell
- Web page: https://patentgrep.com/patent/US5708152A

## CPC

- A61K 47/61: the organic macromolecular compound being a polysaccharide or a derivative thereof
- A61K 8/736: {Chitin; Chitosan; Derivatives thereof}
- A61K 47/36: Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
- A61Q 19/00: Preparations for care of the skin
- C08B 37/003: {Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof}
- C08J 5/18: Manufacture of films or sheets
- A61Q 5/00: Preparations for care of the hair
- A61Q 11/00: Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
- A61Q 15/00: Anti-perspirants or body deodorants (deodorisation of air A61L9/00)
- C08J 2305/08: Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- C08B: POLYSACCHARIDES; DERIVATIVES THEREOF (polysaccharides containing less than six saccharide radicals attached to each other by glycosidic linkages C07H; fermentation or enzyme-using processes C12P19/00; sugar industry C13; production of cellulose D21)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

Chitosan derivatives having structural units of formula I, II and III in random distribution ##STR1## wherein the substituents R.sub.1 are each, independently of one another, H or --Z--R.sub.2 --X, R.sub.3 is H or acetyl, Y is the anion O--Z--R.sub.2 --X, and (a) Z is --CO-- or --SO.sub.2 --, X is --CO.sub.2 H, --CH.sub.2 CO.sub.2 H or --CH.sub.2 PO(OH).sub.2, and R.sub.2 is --CHR.sub.4 CR.sub.5 (OH)--, R.sub.4 is --H, --OH, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkyl, and R.sub.5 is H or C.sub.1 -C.sub.4 alkyl, or (b) Z is --CO--, X is --CO.sub.2 H, and R.sub.2 is --CHR.sub.6 --CHR.sub.7 --CH(OH)-- or --CHR.sub.8 --CHR.sub.9 --CHR.sub.10 --CH(OH)--, R.sub.6, R.sub.7, R.sub.8 and R.sub.10 are each, independently of one another, --H, --OH, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, and R.sub.9 is --H, --OH, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or --CO.sub.2 H, and the esters and salts thereof, which chitosan derivative contains a total of at least 2 structural units and, based on 1 mol of the chitosan derivative, 30 to 100% molar of structural units of formula I, 60 to 0% molar of structural units of formula II, and 30 to 0% molar of structural units of formula III, and the sum of the molar percentages is 100%. These derivatives are suitable for use as humectants and for the prevention of the adherence to and/or formation of solid deposits on inorganic or organic substrates.

## Claims

### Claim 1

A chitosan derivative containing structural units of formulae IX and X in random distribution, ##STR6## wherein the R.sub.12 substituents are each, independently of the other, H or the radical --Z--R.sub.2 --X.sub.3, R.sub.3 is H or acetyl, Z is --CO-- or --SO.sub.2 --, X.sub.3 is --CCl.sub.3, and R.sub.2 is --CHR.sub.4 CR.sub.5 (OH)--, R.sub.4 is --H, --OH, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkyl, and R.sub.5 is H or C.sub.1 -C.sub.4 alkyl, which chitosan derivative contains a total of at least 2 structural units and, based on 1 mol of said chitosan derivative, 30 to 100% molar of structural units of formula IX and 70 to 0% molar of structural units of formula X.

### Claim 2 (depends on 1)

A chitosan derivative according to claim 1, wherein R.sub.12 is H.

### Claim 3 (depends on 1)

A chitosan derivative according to claim 1, whereto Z is --CO--.

### Claim 4 (depends on 1)

A chitosan derivative according to claim 1, wherein R.sub.2 is --CH.sub.2 CH(OH)-- or CH.sub.2 C(CH.sub.3)(OH)--.

### Claim 5 (depends on 1)

A chitosan derivative according to claim 1 which contains a total of at least 4 structural units.

### Claim 6 (depends on 5)

An oligomeric chitosan derivative according to claim 5 which contains 4 to 50 structural units.

### Claim 7 (depends on 6)

An oligomeric chitosan derivative according to claim 6 which contains 6 to 30 structural units.

### Claim 8 (depends on 1)

A chitosan derivative according to claim 1 which contains 50 to 100% molar of structural units of formula IX 50 to 0% molar of structural units of formula X.

### Claim 9 (depends on 1)

A chitosan derivative according to claim 1 which contains 60 to 100% molar of structural units of formula IX and 40 to 0% molar of structural units of formula X.

### Claim 10 (depends on 1)

A process for the preparation of a chitosan derivative according to claim 1 containing structural units of the formulae IX and X in random distribution, which chitosan derivative contains a total of at least 2 structural units and, based on 1 mole of said chitosan derivative, 30 to 100% molar of structural units of formula IX and 70 to 0% molar of structural units of formula X, which process comprises reacting a chitosan containing a total of at least 2 structural units of the formulae IV and V, ##STR7## in random distribution, wherein R.sub.3 is acetyl or H, and said chitosan contains 30 to 100% molar of structural units of formula IV and 70 to 0% molar of structural units of formula V based on 1 mole of chitosan, in the presence of an inert solvent, with at least 30% molar of a lactone of formula VI, based on said chitosan, ##STR8## wherein R.sub.4 is --H, --OH, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkyl, R.sub.5 is H or C.sub.1 -C.sub.4 alkyl, Z.sub.1 is .dbd.CO or .dbd.SO.sub.2 and X.sub.1 is --CCl.sub.3.

### Claim 11 (depends on 10)

A process according to claim 10, wherein the reaction is carried out in the temperature range from 0.degree. to 150.degree. C.

### Claim 12 (depends on 11)

A process according to claim 11, wherein the reaction is carried out in the temperature range from 10.degree. to 120.degree. C.

### Claim 13 (depends on 12)

A process according to claim 12, wherein the reaction is carried out in the temperature range from 20.degree. to 100.degree. C.

### Claim 14 (depends on 10)

A process according to claim 10, wherein the solvent is selected from the group consisting of cyclic ethers, N-alkylated acid amides and lactams, sulfoxides and sulfones.