EP0251905A2 — Esters of alginic acid

Claim 1

Independent Claim 45 words

Total and partial esters of alginic acid with alcohols of the aliphatic, araliphatic, cycloaliphatic, aliphatic-cycloaliphatic and heterocyclic radicals, and salts of said partial esters with inorganic and organic bases, with the proviso that said partial ester is not a partial ester of bivalent aliphatic alcohols.

Claim 2

Dependent Claim 45 words

Total and partial esters of alginic acid with alcohols of the aliphatic, araliphatic, cycloaliphatic, aliphatic-cycloaliphatic and heterocyclic radicals, and salts of said partial esters with inorganic and organic bases, with the proviso that said partial ester is not a partial ester of bivalent aliphatic alcohols.

Claim 3

Dependent Claim 90 words

Alginic acid esters according to claim 1, wherein the alcoholic moiety is a) an aliphatic radical with a maximum of 34 carbon atoms; b) an araliphatic radical with only one benzene ring and in which the aliphatic chain has a maximum of 4 carbon atoms; c) a cycloaliphatic or aliphatic-cycloaliphatic radical which is mono- or polycyclic with a maximum of 34 carbon atoms; or d) a heterocyclic radical with a maximum of 34 carbon atoms and the hetero atoms are selected from the group consisting of oxygen, sulfur and nitrogen.

Claim 4

Dependent Claim 116 words

Alginic acid esters according to claim 2, wherein a) the aliphatic, cycloaliphatic, aliphatic-cycloaliphatic and heterocyclic radicals are substituted by one or two functional groups selected from the group consisting of amino, hydroxy, mercapto, aldehyde, keto, carboxy, hydrocarbyl, dihydrocarbylamino, ether, ester, thioether, thioester, acetal, ketal, carbalkoxy and carbamidic groups and carbamidic groups substituted by one or two alkyl groups, the hydrocarbyl radicals in these functional groups having a maximum of 6 carbon atoms; and b) the araliphatic radicals are substituted in the benzene residue with 1-3 methyl or hydroxy groups or halogen atoms or substituted in the aliphatic portion with one or two functional groups selected from the group consisting of ethyl, diethyl, pyrrolidine and piperidine groups.

Claim 5

Dependent Claim 38 words

Alginic acid esters according to claim 3, wherein a) the carbon chains of said aliphatic, cycloaliphatic, aliphatic-cycloaliphatic and heterocyclic radicals are interrupted in the carbon chain by heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen.

Claim 6

Dependent Claim 65 words

Alginic acid esters according to claim 3, wherein a) said hydrocarbyl radicals of said functional groups are C 1-14 alkyl groups; b) said amino or substituted carbamidic groups are C 1-8 alkylene amine or C 1-8 alkylene carbamidic groups; c) said cycloaliphatic, aliphaticcycloaliphatic or heterocyclic moieties are monocyclic with a maximum of 12 carbon atoms and the ring has between 5 and 7 carbon atoms.

Claim 7

Dependent Claim 91 words

Alginic acid esters according to claim 2, wherein a) said aliphatic radical derives from a member selected from the group consisting of ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, pentyl, hexyl or octyl alcohol, glycerin, tartronic alcohol, lactic acids, glycolic acid, malic acid, a tartaric acid, a citric acid, aminoethanol, aminopropanol, n-aminobutanol or their dimethyl or diethyl derivatives in the amino function, choline, pyrrolidinylethanol, piperidinyl-ethanol, piperazinyl-ethanol, piperazinyl-n-propyl, piperazinyl-n-butyl alcohol, monothioethylenglycol or its lower alkyl derivatives in the mercapto function, cetyl alcohol, myricyl alcohol, citronellol, geraniol, nerol, nerolidol, linalool, farnesol and phytol.

Claim 8

Dependent Claim 110 words

Alginic acid esters according to claim 1, wherein said alcoholic moiety derives from a member selected from the group consisting of benzyl alcohol, phenethyl alcohol, ephedrine, adrenalin, from the group formed by cyclohexanol, cyclohexanediol, 1,2,3 cyclohexanetriol, 1,3,5 cyclohexanetriol, inositol, carvomenthol, menthol, α and γ-terpineol, 1-terpinenol, 4-terpinenol, piperitol, 1,4- and 1,8-terpin, thujanol, sabinol, pinol hydrate, D and L-borneol, D- and L-isoborneol, sterols, cholic acids, steroids, cholesterol, dihydrocholesterol, epidihydrocholesterol, coprostanol, epicoprostanol, sitosterol, stigmasterol, ergosterol, cholic acid, deoxycholic acid, lithocholic acid, estriol, estradiol, estratriol, equilenin, equilin, the methyl derivatives in position 7 of estriol, estradiol, estratriol, equilenin or equilin, and ethynyl or propynyl derivatives in position 17 of estriol, estradiol, estratriol or equilin.

Claim 9

Dependent Claim 74 words

Alginic acid esters according to claim 1, wherein the alcoholic moiety is a member selected from the group consisting of pregnenolone, pregnanediol, testosterone, 17-α-methyltestosterone, 1,2-dihydro testosterone, 17-α-methyl-1,2-dehydrotestosterone, 17-α-ethynyltestosterone, 17α-propynyltestosterone, norgestrel, hydroxyprogesterone, 19-nortestosterone, 19 nor-17α-methyl-testosterone, 19-nor-17α-ethynyltestostrone, cortisone, hydrocortisone, prednisone, prednisolone, fludrocortisone, dexamethasone, betamethasone, corticosterone, deoxycorticosterone, paramethasone, flumethasone, fluocinolone, the acetonide of fluocinolone, fluprednylidene, clobetasol, beclomethasone, genins of cardioactive glycosides, axerophthol, calciferol and vitamins D₂, D₃ and D₄, aneurine, lactoflavine, ascorbic acid, riboflavine, thiamine, panthothenic acid.

Claim 10

Dependent Claim 53 words

Alginic acid esters according to claim 1, wherein the alcoholic moiety is a member selected from the group consisting of alkaloids, phenylethylamines, phenothiazine drugs, thioaxanthene drugs, anticonvulsivants, antipsychotics, antiemetics, analgesics, hypnotics, anorexics, tranquilizers, muscle relaxants, coronary vasodilators, adrenergic blockers, narcotic antagonists, antineoplastics, antibiotics, antivirals, peripheral vasodilators, carbonic anhydrase inhibitors, antiasthmatics, anti-inflammatories and sulfamidics.

Claim 11

Dependent Claim 20 words

Alginic acid esters according to one of claims 1-9, in which all the carboxy groups of alginic acid are esterified.

Claim 12

Dependent Claim 30 words

Alginic acid esters according to one of the claims 1-9, in which at least 5% and at the most 95% of all the carboxy groups of alginic acid are esterified.

Claim 13

Dependent Claim 21 words

Salts of partial esters according to any one of claims 1-9 deriving from alkaline and alkaline earth metals, magnesium or aluminium.

Claim 14

Dependent Claim 20 words

Salts of partial esters according to any one of claims 1-9 deriving from aliphatic, araliphatic, cycloaliphatic or heterocyclic amine bases.

Claim 15

Dependent Claim 16 words

Salts of partial esters according to claim 13, in which the amines are therapeutically acceptable bases.

Claim 16

Dependent Claim 59 words

Salts of partial esters according to claim 14 in which the amines are chosen from the group consisting of alkaloids, peptides, phenothiazine, benzodiazepine, thioxanthene, hormones, vitamins, anticonvulsivants, antipsychotics, antiemetics, anesthetics, hypnotics, anorexics, tranquilizers, muscle relaxants, coronary vasodilators, antineoplastics, antibiotics, antibacterials, antivirals, antimalarials, carbonic anhydrase inhibitors, non-steriod anti-inflammatories, vasoconstrictors, cholinergic agonists, cholinergic antagonists, adrenergic agonists, adrenergic blockers and narcotic antagonists.

Claim 17

Dependent Claim 70 words

Salts of partial esters according to claim 13, in which the amines are pharmacologically inactive and are selected from the group consisting of: a) mono- di- and tri-allylamines with a maximum of 8 carbon atoms; b) arylalkylamines with a maximum of 8 carbon atoms in the aliphatic portion and having a benzene ring as the aromatic portion; and c) alkylene amines with cycles of between 4 and 6 carbon atoms.

Claim 18

Dependent Claim 63 words

Salts of partial esters according to claim 16, wherein a) said arylalkylamines are substituted with between 1 and 3 methyl groups, hydroxy groups or halogen atoms; b) said alkylene amines are interrupted in the carbon chain by at least one oxygen or sulfur atom; or c) said mono-, di- or tri-allylamines, arylalkylamines or alkylene amines are substituted with amino or hydroxy functional groups.

Claim 19

Dependent Claim 44 words

Pharmaceutical compositions comprising as an active ingredient an ester or one of its salts according to any one of claims 1-17, or a partial ester of a bivalent aliphatic alcohol of alginic acid, or one of its salts, together with a pharmaceutically acceptable excipient.

Claim 20

Dependent Claim 47 words

Pharmaceutical preparations containing: a) a pharmacologically active substance or an association of pharmacologically active substances and b) a carrying vehicle constituted by a total or partial ester of alginic acid with an alcoholic moiety or by the salts of such partial esters with inorganic or organic bases.

Claim 21

Dependent Claim 47 words

Pharmaceutical preparations containing: a) a pharmacologically active substance or an association of pharmacologically active substances and b) a carrying vehicle constituted by a total or partial ester of alginic acid with an alcoholic moiety or by the salts of such partial esters with inorganic or organic bases.

Claim 22

Dependent Claim 26 words

Pharmaceutical preparations according to claim 19, wherein at least one of said alcoholic moiety or said inorganic or organic bases derives from a therapeutically active compound.

Claim 23

Dependent Claim 112 words

Pharmaceutical preparations according to claim 20, wherein a) said alcoholic moiety is a member selected from the group consisting of an aliphatic radical with a maximum of 34 carbon atoms, an araliphatic radical with only one benzene ring and in which the aliphatic chain has a maximum of 4 carbon atoms, a cycloaliphatic or aliphatic-cycloaliphatic radical which is mono- or polycyclic with a maximum of 34 carbon atoms, and a heterocyclic radical with a maximum of 34 carbon atoms and the hetero atoms are selected from the group consisting of oxygen, sulfur and nitrogen; and b) said bases are selected from the group consisting of aliphatic, araliphatic, cycloaliphatic and heterocyclic amine bases.

Claim 24

Dependent Claim 32 words

A cosmetic article containing a total or partial ester of alginic acid or a salt thereof according to claim l, or a partial ester of alginic acid with a bivalent aliphatic alcohol.

Claim 25

Dependent Claim 23 words

Sanitary or surgical articles comprising at least one total or partial ester of alginic acid or a salt thereof according to claim 1.

Claim 26

Dependent Claim 16 words

Sanitary or surgical articles according to claim 23, wherein the article is a film or thread.

Claim 27

Dependent Claim 16 words

A method for using films of alginic acid esters according to claim 24 as artificial skin.

Claim 28

Dependent Claim 19 words

A method for using threads of alginic acid esters according to claim 24 as suture threads in surgical operations.

Claim 29

Dependent Claim 13 words

Alimentary articles comprising at least one alginic acid ester according to claim 1.

Claim 30

Dependent Claim 22 words

Articles for industrial use in the textile, printing or paper industries comprising at least one alginic acid ester according to claim 1.

Claim 31

Dependent Claim 15 words

Household articles or detergents comprising at least an alginic acid ester according to claim 1.

Claim 32

Dependent Claim 62 words

A procedure for the preparation of films or threads of alginic esters according to claim 24 in which the alginic ester is dissolved in a first organic solvent, the solution is made into sheet or thread form respectively, and then the first organic solvent is eliminated by treatment with another suitable organic or aqueous solvent which is soluble in the first solvent.

Claim 33

Dependent Claim 42 words

A process for the preparation of partial or total esters of alginic acid which comprises reacting in an aprotic solvent, a quaternary ammonium salt of alginic acid with an etherifying agent and, optionally, salifying any free carboxy groups in the obtained esters.

Claim 34

Dependent Claim 42 words

A process for the preparation of partial or total esters of alginic acid which comprises reacting in an aprotic solvent, a quaternary ammonium salt of alginic acid with an etherifying agent and, optionally, salifying any free carboxy groups in the obtained esters.

Claim 35

Dependent Claim 17 words

A process according to claim 31, wherein the ester produced is a partial ester of alginic acid.

Claim 36

Dependent Claim 27 words

A process according to claim 32, which further comprises reacting said partial ester with an alkali salt to salify the free carboxyl groups in said partial ester.

Claim 37

Dependent Claim 17 words

A process according to any one of claims 31-33, wherein said organic solvent is an aprotic solvent.

Claim 38

Dependent Claim 12 words

A process according to claim 34, wherein said aprotic solvent is dimethylsulfoxide.

Claim 39

Dependent Claim 23 words

A process according to any one of claims 34-35, wherein said quaternary ammonium salt is a lower tetraalkyl ammonium salt of alginic acid.

Claim 40

Dependent Claim 14 words

A process according to claim 36, wherein said quaternary ammonium salt is tetrabutylammonium alginate.

Claim 41

Dependent Claim 24 words

A process according to any one of claims 36-37, which further comprises adding an organic solvent to precipitate out said ester of alginic acid.

Claim 42

Dependent Claim 18 words

A process according to claim 38, which further comprises recovering, washing and drying said ester of alginic acid.

Claim 43

Dependent Claim 41 words

A process according to claim 38, wherein said quaternary ammonium salt of alginic acid is prepared by passing an alkali salt of alginic acid through a quaternary ammonium salt ion exchange resin; and recovering said quaternary ammonium salt of alginic acid.

Claim 44

Dependent Claim 19 words

A process according to claim 40, wherein said quaternary ammonium salt ion exchange resin is a sulfonic acid resin.

Claim 45

Dependent Claim 20 words

A process according to claim 41, wherein said quaternary ammonium salt of sulfonic acid is a C₁-C₆ tetra-alkyl ammonium salt.

Claim 46

Dependent Claim 20 words

A process according to claim 33, wherein said alkali salt is selected from the group consisting of sodium or potassium.

Claim 47

Dependent Claim 42 words

A process according to claim 31, wherein said etherifying agent is a compound of the formula A-X (I) wherein A is a radical selected from the group consisting of aliphatic, araliphatic, cycloaliphatic, aliphatic-cycloaliphatic and heterocyclic radicals and X is a halogen atom.

Claim 48

Dependent Claim 22 words

A process according to claim 44 wherein A is selected from the group consisting of methyl, ethyl, i-propyl, t-butyl and benzyl radicals.

Claim 49

Dependent Claim 34 words

A process for preparing partial or total esters of alginic acid which comprises reacting alginic acid with a stoichiometric quantity of an alcohol, said stoichiometric quantity being determined by the degree of esterification desired.

Claim 50

Dependent Claim 34 words

A process for preparing partial or total esters of alginic acid which comprises reacting alginic acid with a stoichiometric quantity of an alcohol, said stoichiometric quantity being determined by the degree of esterification desired.

Claim 51

Dependent Claim 13 words

A process according to claim 46 wherein said alcohol is an aliphatic alcohol.

Claim 52

Dependent Claim 13 words

A process according to claim 46 wherein said alcohol is an araliphatic alcohol.

Claim 53

Dependent Claim 13 words

A process according to claim 46 wherein said alcohol is a cycloaliphatic alcohol.

Claim 54

Dependent Claim 13 words

A process according to claim 46 wherein said alcohol is a heterocyclic alcohol.

Esters of alginic acid

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