IE44757B1 - Sweeteners - Google Patents

Abstract

At least one compound of the formula I, in which the substituents R<1>, R<2>, R<3>, R<4> and R<5> have the meanings given in Patent Claim 1, is added as sweetening agent to the substance to be sweetened. A mixture of such compounds or a combination of at least one compound of the formula I with a solid or liquid extender or carrier can also be used. The compounds of the formula I are derivatives of sucrose, but are much sweeter than sucrose although they are comparable to it with respect to quality, and they are comparable to saccharin with respect to the intensity of the sweetening action. The method is suitable both for sweetening foodstuffs and also luxury foods, stimulants and drugs. The compounds of the formula I are not absorbed by the human body and do not have any disadvantageous action on the human organism in the widest range of conventional use concentrations.

Description

» This invention relates to sweeteners for ingestible products, oral compositions and sweetening compositions.

By an ingestible product there is meant one which in the ordinary course of use is intended to be swallowed, for instance a foodstuff or beverage, or an orally administered pharmaceutical composition. By an oral composition there is meant one which in the ordinary course of use is not intended to be ingested as such, but is taken into the mouth for the treatment of the throat or buccal cavity, for instance a toothpaste, tooth powder, mouth wash, gargle, troche, dental lotion or chewing gum. By a sweetening composition there is meant a composition which is not itself taken orally, either to be ingested or held in the mouth, but instead is intended to be added to other ingestible products or oral compositions to render them sweet or to increase their sweetness.

Although sucrose is still the most widely used sweetening agent, many efforts have been made to find substantially sweeter alternatives which could be used when it is desired to combine a high degree of sweetness with a low calorie content and/or a low risk of dental caries, for example in dietetic products and in the manufacture of soft drinks. The two most successful non-sucrose sweeteners (that is to say sweeteners comprising a compound other than sucrose itself) to date have been saccharin and cyclamate, having respectively about 200 and about 30 times the sweetening power of sucrose, but the use I of these sweeteners, particularly cyclamate, has recently been Sv restricted or banned in some countries because of doubts about their safety. Saccharin also suffers from the disadvantage of an unpleasantly bitter after-taste which can be detected by many people.

More recently, many other non-sucrose sweeteners have been investigated, some of natural origin and others synthetic, covering a wide range of chemical structures. These compounds have included proteins, such as moneliin, thaumatin and miraculin, dipeptides such as aspartame, and dihydrochalcones such as neohesperidin dihydrochalcone. However, apart from the difficulties of synthesizing or extracting such sweeteners, they do not necessarily possess the same quality of sweetness as sucrose: in particular, as compared with sucrose, the sweetness may be slow in onset and relatively lingering, and there may be a liquorice-like or other after-taste, making the sweetener unsuitable as a direct replacement for sucrose unless these differences can be masked.

Although numerous sweeteners of widely diverse chemical structures have now been investigated, it is significant to note that sweetness substantially greater than that of sucrose has not been discovered in any derivative of sucrose or in any other carbohydrate: when an intensely sweet substance has been discovered, such as saccharin, cyclamate and the other non-sucrose sweeteners already mentioned, its structure has always been radically different, from th.-n of sucrose. Indeed, it is known that the presence of some siibsUuiciii.··. on the sucrose molecule can, in fact, destroy its sweetness and even .. 44757 impart a bitter taste.

Most surprisingly, and in complete contrast to previous knowledge about non-sucrose sweeteners, we have now discovered that certain derivatives of sucrose and of a sucrose isomer are very much sweeter than sucrose itself, their sweetness being comparable in intensity with that of saccharin, but having a quality similar to that of sucrose.

According to the present invention we provide as sweetening agents sucrose derivatives of the general formula in which R represents a hydroxy group or a chlorine atom; 3 R and R respectively represent a hydroxy group and a hydrogen atom, a chlorine atom and a hydrogen atom, or a hydrogen atom and a chlorine atom, the t 4-position being in the D-configuration; 1 R represents a hydroxy group; or, if at least two of R , R2, R3 and R^ represent chlorine atoms, R^ I represents a hydroxy group or a chlorine atom; and ΰ R represents a hydroxy group oi' a chlorine atom; 3 provided that at least one of R , R, and R represents a chlorine atom.

The compounds of formula (I) can be used as sweetening agents in any conventional way, including the sweetening of ingestibie products (as previously defined), for example foodstuffs, beverages and orally administered pharmaceutical compositions, and of oral compositions (as previously defined), for example toothpastes, chewing gums and mouth washes. They can also be used, with conventional liquid or solid extenders and carriers, in sweetening compositions (as previously defined).

The extender or carrier comprises any suitable vehicle for the sucrose derivative of the general formula (I) so that it can be formulated in a composition which can conveniently be used for sweetening other products, for example granules, tablets or a solution in a dropper pack.

/The extender or carrier may thus include, for example, conventional water-dispersible tabletting ingredients, such as starch, lactose and sucrose itself; low-density bulking agents to provide a granular sweetening composition having a volume per unit sweetness equivalent to that of sucrose, for example, spray dried maltodextrins; and aqueous solutions containing adjuvants such as stabilizing agents, colouring agents and viscosity-adjusting agents. ¢47.87 Beverages, such as soft drinks, containing a sucrose derivative of the general formula (I) may be formulated either as sugar-free dietetic products, or sugar-reduced products containing the minimum amount of sugar required by law. In the absence of sugar it is desirable to add further agents to provide a mouth feel similar to that provided by sugar, for example pectin or a vegetable gum.

I Thus, pectin may be added at a level of from 0.1 to 0.15% in a bottling syrup.

A number of compounds of the general formula (I) which may 10 be used according to the present invention are shown in the following Table.

Table Compound No, R1 R2 R3 /1 Rx R5 Approximate sxveetness (x sucrose!1 1 Cl OH H OH OH 20 2 OH H Cl OH OH 5 5 3 Cl H Cl OH OH 600 4 Cl OH H OH Cl 300 5 Cl H Cl OH Cl 2000 6 OH H Cl Cl Cl 4 7 Cl OH H Cl Cl 100 10 8 Cl H Cl Cl Ci 200 9 Cl Cl H Cl Cl 100 * Sweetness Evaluation The sweetness is evaluated in aqueous solution, by comparison with a 10% by weight aqueous solution of sucrose. The results were obtained from a small taste panel and are, therefore, not statistically accurate, but indicate the approximate order of sweetness. . 44757 The compounds in Table 1 are as follows (the systematic nomenclature is given first, followed by a trivial name based on ''galactosuerose'1 in those cases where a 4-chloro substituent is present): 1. l'-chloro-l' -deoxysucrose 2. 4-ehloro-4~de.oxy-a-D-galactopyranosyl-0-Dfructofuranoside [i.e. 4-chloro-4-deoxygalactosucrose1 « 3. 4-chloro-4-deoxy-«-D-galactopyranosyl-l-chloro-ldeoxy-0-D-fructofuranoside [i.e. 4, l'-dichloro-4,1'dide oxygalactosucr ose] 4. . 1', 6-dichloro-l’, 6' -dideoxysucrose . 4-chloro-4-deoxy-a-D-galactopyranosyl-l, 6-dichloro1,6-dideoxy-p-D-fruclofurahosidc [i.e. 4,l',6'-trichloro-4,1', 6' -trideoxygalactosucrose] 6. 4, 6-diehloro-4,6-dideoxy-a-D-galactopyranoSyl-6chloro-6-deoxy-/3-D-fructofuranoside [i.e.. 4,6,6'trichloro-4,6, 6'-trideoxygalactosucrose] 7. 6,1', 6'-trichloro-6,1', C-trideoxysucrose · 8. 4,6-dichloro-4,6-dideoxy-a-D-galactopyranosyl-l,6, dichloro-l,6^dideoxy-(3-D-fructofuranoside [i.e. 4,6,1',6'-tetrachloro-4,6,1',6'-tetradeoxygalactosucrosel 9. 4,6,1', 6' -tetrachloio-4i 6,ll, 6’ -tetradeoXysucrose.

From Table 1 it may be seen that chloro substituents at the 4-, 1‘- and 6'- positions are effective in inducing sweetness, A -· /'. · combination of two such substituents is synergistic and in general raises , - 8 the sweetness by approximately one order of magnitude rather than being simply additive. Thus, for example, a 1'-chloro substituent by itself gives a sweetness of 20x and a 4,3-chloro substituent by itself a sweetness of 4x. However, a 4,1’-dichloro combination gives a sweetness of 600x and a 1', 6'-dichloro combination gives a sweetness of 500x, Similarly, a combination of all three chloro substituents raises the sweetness by approximately one more order, the 4,1', 6'-trichloro derivative having a sweetness of 2000x. (All sweetnesses expressed as multiples of that oi sucrose).

In contrast, a 6-chloro substituent is disadvantageous, and causes a reduction in sweetness by antagonising the action of the other substituents. For this reason, a 6-chloro substituent - R in formula (I) - may only be present when at least two other chloro substituents are present. in general, the 6-chloro-substituted compounds are not preferred for this reason - the most sweet compounds containing 4,1'- and 6'-chloro substituents.

The remarkable sweetness of the compounds Of formula (I) is combined with an (lethal dose 50%) which, in the case of compound 5 in Table 1, for example, is in excess of 16g/kg in mice, that being the largest dose which can be administered in practice.

Most of the compounds of the general formula (I) arc- known and can be prepared by the synthetic routes disclosed in the chemical literature. However, none of the known compounds has previously been recognised as possessing any useful sweetness.

Thus, Compound 5 is reported in Carbohyd. Res., 40, (1975), 5 285; Compound 6 in Carbohyd, Res., 44, (1975), 37; and Compound 7 in Carbohyd. Res., 25, (1972), 504 and ibid 44, (1975), 12-13. Compound 2 is reported in Carbohyd. Res., 40, (1975), 285-298.

Compounds 4 and 8 are claimed in British Patent Specification No. 1,543,168 · ’ AU of the compounds of the general formula (I), both new and old, may be prepared by reaction of a sucrose ester, having free 1 hydroxy groups in the portions required to be chlorinated, with sulphuryl chloride to obtain the corresponding chlorosulphate derivative.

This, on treatment with a source of chloride ions such as lithium chloride, in an amide solvent such as hexamethyl phosphoric triamide, yields the chlorinated sucrose ester. Hydrolysis of the chloro-ester, e.g. using sodium methoxide in dry methanol, then liberates the free chlorosucrose. The reaction with sulphuryl chloride is conveniently effected at a reduced temperature in an inert solvent in the presence of a base, for example chloroform containing pyridine.

A similar method can be used for further chlorinating an already chlorinated sucrose derivative.

Xn general 4-chloro-sucrose derivatives can be obtained by reaction of the 4-chloro-galactosucrose analogue with a source of chloride ions at an elevated temperature, e.g. 100-150°C, preferably in the presence of a catalytic amount of iodine.

The following Examples illustrate the invention further {temperatures are given in degrees centigrade).

Example 1 l'-chloro-l'-deoxysucrose (Compound 1) a) 1' £W£({?y;i{^d^xysucrqse_hegta-acetate A solution of 2, 3,4, 6, 3', 4', 6' -hepta-O-acetylsucrose (2g) in a mixture of pyridine (10 ml) and chloroform (30 ml) was treated with sulphuryl chloride (2 ml) at -75° for 45 minutes. The reaction mixture was taken up in ice-cold sulphuric acid (10%, 200 ml) and dichloromethane (200 ml) and shaken vigorously. The organic layer was then successively washed with water, aqueous sodium hydrogen carbonate and water, and then dried (NagSO^). The solution was concentrated and then extracted with ether. The insoluble material was filtered off and the filtrate concentrated to give the corresponding I-chlorosulphate derivative (2.1 g).

This syrupy residue (2g) was then treated with lithium chloride (2g) in hexamethyl phosphoric triamide (IIMPA) (10 ml) at U0° for 24 hours. The reaction mixture was poured into ice-water, and ihe precipitate formed was collected, washed v/ith water, and taken up in 44757 ether. The organic layer was dried over sodium sulphate,concentrated and eluted from a silica gel column with ether - light petroleum (1:1) to give the l'-ehloro hepta-acetate as an amorphous powder («1 + 55. 0° (c 1.2, CHC1„); n.m.r. data: ~ 4.29 (d, J 3,5Hz, H-l) .11 (dd, J2 ’ 10. 0Hz, H-2); 4. 56 (t. 4 9. 5Hz, H-3); 4. 94 (t, g 9.5Hz, H-4); 4.32 (d, Jg, 4, 6. 5Hz, H-3'); 4.60 (£, g| 6. 5Hz, H-4'); 7. 84-8. 01 (7 Ac). Mass spectral data: ((a) indicates ions due to hexapyranosyl cation and (b) a 3 :1 doublet (1C1) due to ketofuranosyl]: m/e 331 a, 307 b, 187 b, 169 a, 145 b, 109 a.

Analysis calculated for C^HggClΟχ? ; C, 47. 7; H, 5.4; Cl, 5.4% Found . : C, 47. 5; H, 5. 6; Cl, 5.7%.

I (b) i'^chloro-£'j;d^eox£sucrose_ A solution of the above intermediate (lg) in dry methanol (10 ml) was treated with a catalytic amount of M sodium methoxide in I methanol at room temperature for 5 hours. T.I. c. (dichloromethane I methanol, 3 :1) showed a slow-moving product. The solution was deionized by shaking with Ainberlyst - 15 (a polystyrene sulphonic acid Amberlyst jjeing a Trade Mark resin), in TI form) concentrated, and purified by shaking an aqueous jo solution of the syrup with petrol. The aqueous layer was then concentrated and dried under vacuum to give l'-chloro-l'-deoxysucrose My, + 57. 8° (c 0. 7, water).

Analysis calculated for C,„iI_ClO,„ : C, 39. 9; H, 5. 9; Cl, 9. 8¾ la fl XU : C, 39.7; II, 6.1; Cl, 9. 7%.

Found - 12 Example 2 4,I1-dichloro-4,1'-dideoxygalactosucrose (Compound 3) (a) 2 JL 6-Tri-O_-acetyl-4^chloro-_pgdejwy-_a_^D^alactonyrmiosjd4^ di-O-aeetyl- δ-O - benz oyl-^l_-_ehlor o_-_l 2.

A solution of 2, 3, 6,3', 4'-penta-O-acetyl-6'-O-beazoylsucrose (2g) in a mixture of pyridine (10 ml) and chloroform (30 ml) was treated with sulphuryl chloride (2 ml) at -75° for 45 minutes. The reaction mixture was poured into ice-cold sulphuric acid (10%, 200 ml) with vigorous shaking and then extracted v/ith dichloromethane. The organic layer was washed successively with water, aqueous sodium hydrogen carbonate, and water, and dried (Na^SO^). The solution was concentrated and extracted with ether. The insoluble material was filtered of? and the filtrate concentrated to give the ehlorosulphate (2. lg). This intermediate was then treated with lithium chloride as in Example 1 to give the above-named chloro intermediate. (b) 4^hloro’JlklLblpro-lydeoxyy β_~ D -irtlStofui^nosidi· A solution of the above intermediate from (a) (lg) in dry methanol was treated with a catalytic amount of M -sodium methoxide in methanol at room temperature for 5 hours, T.l.c. (dichloromethane methanol, 4:1) showed one product. The reaction was worked up as described in Example 1(b) to give the title product as a syrup, + 49. 6° (c 0.7, water).

Analysis calculated for Cj H Cl Og : C, 38. 0; H, 5. 3; Cl, 18. 7% Pound : C, 35.7; H, 6. 0; Cl, 20,4%.

By a similar method 1', 6'-dichloro-l', 6'-dideoxysucrose (Compound 4) was prepared: [«]D + 67° (e 1. 0,. methanol).

Analysis calculated for c12H20C12O9 : C, 38. 0; H, 5. 3; Cl, 18. 7% Found : C, 37.7; H, 5. 2; Cl, 17.1%.

Hexa-acetate - white solid foam, + 51. 7° (c 1. 0, CHClg) Mass spectrometry m/e 331 and 283 (2 Cl). Characterized by reductive dehalogenation with Raney Nickel, Hg and KOH to 1', 6'-dideoxysucrose hexaacetate - a thick colourless syrup; [a] + 25. 5° (c 1.0, CHC1 ).

JJ u 100 Hz N.M.R. (σθϋθ Rvalues) - H-l, 4. 36 d (^ 2 3. 5 Hz); H-2, 4.99 q (J_ „ 10. 5 Hz); H-3, 4.17 t (J„ ’ 10. 0 Hz); H-4, 4.71 t ώ ,0 u t t: (J . c 10. 0 IIz); Π-1', 8. 58 s; H-6', 8. 60 d. 4,5 lixample 3 1, 6-dichloro-l, 6-dideoxy-(3-D-fructofuranosyl-4, 6-dichloro15 4, G-dideoxy-n-D-galaetopyranosidc (Compound 8) Λ solution of 0,1', 0' -trichloro-G, 1', 0' -trideoxysucrosc (3g) in pyridine (70 nil) was treated with sulphuryl chloride (35 ml) in dry chloroform (100 ml) at -75° for 3 hours. The solution was stirred at 0 to -5° for 2 hours and then at room temperature for 24 hours. The reaction mixture was then diluted with dichloromethane (100 ml) and washed successively with ice-cold sulphuric acid (10%, 250 ml), water, aqueous sodium hydrogen carbonate, and water. The organic iayei’ was dried over sodium sulphate and concentrated to give a syrup. Tho syrupy residue was dissolved in methanol (100 ml) and dechlorosulphated by means of excess barium carbonate and a catalytic amount of socbum iodide. The inorganic residue was filtered off and the filtrate concentrated to a syrup. T.I. c. (chloroform - methanol, 4:1) showed 5 the 4, 6,1', S'-tstrachloro-4, 6,1', S'-tetradeoxygalactosucrose as the major product. A fast-moving minor product, probably a pentachloro derivative, was also observed. Purification on a column of silica gel, using chloroform - acetone (5:1) gave the tetrachloro derivative in 90% yield.

Precisely equivalent results were obtained by repeating the above procedure but starting from 1', 6' -dichloro-1', 6'-dideoxysucrose or 1*-chloro-1'-deoxysucrose, instead of the 6,1', 6' -trichloro-6, l1,6' trideoxysucrose. [ff]p + 89° (c 1.0, methanol). Mass spectroscopy: m/e 199 (2-C1).

Tetra-acetate - white solid foam, [e]^ + 98.5° (e 1. 0, CIICl.p, 100 MHz N.M.R. (CDClg, V values) - 4. 28 d (H-l), 5, 25 q (H-4), 4. 30 d (H-3'), 4. 55 t (H-41) J. ,. 3. 5 Hz; J 3. 0 Hz; J r 1. 5 Hz; 1,6 w t Q Qf J Jg, 6.5 Hz; J^, g, 6.5 Hz. Mass spectrometry m/e 283 (2 Cl).

Tetra-mes.yiaie - very pale yellow crystals from diehloromethane - ethanol; 111. p. 120-121°; [«J^ + 65. 5° (c 1. 0, CliCI,/ 100 MHz N. M.R. (CDC1 , f values) Π-1 4.18 d (J1 g 3. 5 Hz); H-2 5. 06 q (J2 3 10 Hz); II-3 4.77 q (Jg 4 3. 5 Hz); H-4 5. 20 q (J4 5 1. 5 Hz); H-3· 4. 39 d (Jg, 4, 7. 0 Hz); H-4' 4. 65 t (J4, g, 7. 0 Hz); Mass spectrometry m/e 355 (2 Cl).

Example 4 4, 6,1', 6'-tetrachlorosucrose (Compound 9) To a solution of 4,6,6' -trichloro-4, 6,6' -trideoxy-2, 3, 3', 4' tetra-O-acetylgalactosucrose l'-O-monomesitylenesulphonate (lg) in D. M, F. (15 ml) was added excess of lithium chloride (2g) and a catalytic amount of iodine (50 mg) and the mixture was heated at ίθ 140-145° in an oil-bath for 18 hours, T.l.c. (benzene - ethylacetate 3; 1) indicated the presence of a major product moving faster than the starting material. The reaction mixture was cooled, poured into icecold water aj?d then extracted with ethyl acetate. The organic extract was washed thoroughly, first with 5% sodium thiosulphate solution and then with water, and dried. The ethyl acetate was evaporated off and the residue was treated with methanol containing a catalytic amount of sodium methoxide.

T.l.c. (chloroform/acetone/methanol/water, : 20:20: 3) now showed the presence of a faster-moving minor product and a slower-moving major product - both having very similar mobilities and the latter corresponding to 4, 6,1', 6' -tetradeoxy-galactosucrose (Compound 8) (mixed 1.1. c.). The mixture was fractionated over a column of silica gel using chloroform-methanol (10:1) as eluent.

Although complete separation was not achieved because of the close mobilities of the two components, the first few fractions contained 4,6,1', 6' -tetrachloro-4,6,1', 6' -tetradeoxy-sucrose which was obtained as a white solid Mj-j + 45° (e 1. 0, MeOH). The structure was confirmed by n. m. r. and mass spectrometry of the following derivatives: 5 Tetra-acetate - syrup, + 30, 5° (c 1. 0 CHC1O) Ν, M. R, ' U ΰ (CD, r values) - H-l, 4. 39 d (J, „ 4. 35 Hz); H-2, 5,14 q(J„ „ 10 Hz); b b 1,2 Z, a H-3, 4, 27 t (Jg 4 10 Hz); H-4, 6,1 t (J4 g 10 Hz); H-3', 4.20 d (J3, 4, 9. 6 Hz); H-4', 4. 62 t (J^ g, 6. 0 Hz).

Tetra-mesylate - white crystalline compound m.p. 187° (dichloromethane - methanol) ft?)p + 29.9° (c 1. 0, acetone).

Example 5 Sweetening tablets for beverages, etc,, Each tablet contains: Compound 3 8 mg or Compound 5 2 mg together with a dispersable tablet base (ca. 60mg) containing sucrose, gum arabic and magnesium stearate, and is equivalent in sweetness fe about 4. 5 g sucrose.

Example 6 Bulked sweetener A bulked sweetener having the same sweetness as an equivalent volume of sucrose (granulated sugar) is prepared by mixing the following v ingredients and spray-drying to a bulk density of 0. 2 g/cc: maltodextrin solution containing dry weight 222. 2 g Compound3 1.7 g (or Compound 5 0.5 g).

The resulting composition has a sweetening power equivalent to approximately 2 kilograms of sugar.

Example 7 Reduced calorie cola drink containing sugar Ingredients to prepare 100 ml bottling syrup: Compound 3 80 mg (or Compound 5 . 20 mg Sugar 60 g Benzoic acid 3 5 mg Phosphoric acid (cone.) 1 ml Cola flavour 1.1 ml Colour ad-lib.

Make up to 100 ml with mineral water.· This syrup may then be added in 25 ml doses to carbonated 225 ml aliquots of chilled mineral water.

. Example 8 Carbonated low calorie lemonade (sugar-free) Ingredients to prepare 100 ml syrup: Compound 3 100 mg 5 (or Compound 5 19 mg ) Benzoic acid 35 mg Citric acid (dry base) 1.67 g Lemon essence 0.8 g Make up to 100 ml in mineral water. 10 This syrup can be added in 25 ml doses to 225 ml aliquots carbonated chilled mineral water. Example 9 Toothpaste % b.y weight 15 Dibasic calcium phosphate 50% Glycerol 20% Sodium lauryl sulphate 2. 5% Spearmint oil 2.5% Gum tragacanth 1.0% 20 Compound 3 0. 03% Water 23. 97% The ingredients are mixed to produce a spearmint flavoured toothpaste of acceptable sweetness but free from sugar or saccharin.

Example 10 Chewing Gum part by weight Polyvinyl acetate 20 Butyl phthalylbutylglycolate 3 Polyisobutylene 3 Microcrystalline wax 2 Calcium carbonate 2 Flavouring/ aroma 1 Compound 3 0, 07 Glucose 10 The above chewing gum base can be cut into conventional tablets or strips. <3 ? 5y

Claims (20)

1. Claims: 1. A method of sweetening a substance, comprising incorporating therein a compound of the general formula (I) 2. 3 R and R respectively represent a hydroxy group and a hydrogen atom, a chlorine atom and a hydrogen atom, or a hydrogen atom and a chlorine atom, the 4-position being in the D-configuration; 4 1 R represents a hydroxy group; or, if at least two of R , 2 3 5 4 R , R and R represent chlorine atoms, R represents a hydroxy group or a chlorine atom; and R represents a hydroxy group or a chlorine atom; 12 3 provided that at least one of R , R , ' and R represents a chlorine atom.

2. A method according to Claim 1, in which the compound of formula (I) has the substituent representing a chlorine atom.

3. A method according to Claim 1 or Claim 2, in which the compound of formula (I) has the substituent R representing a hydroxy 5 group.

4. A method according to Claim 1, in which the compound of formula (I) is 1', 6' -dichloro-1', 6'-dideoxysucrose; 4,6-dichloro-4, 6dide oxy-e-D -galactopyranosyl- 6 -chloro -6 -de oxy-β -D -f ructofuranoside; 6,1', 6' -trichloro-6,1', 6'-trideoxysucrose; or 4,6-dichloro-4, 6Ίθ dideoxy-ff-D-galactopyranosyl-1, 6-dichloro-l, 6-dideoxy~0-D-fructofuranoside.

5. A method according to Claim 1, in which the compound of formula (1) is 1'-chloro-1'-deoxysucrose; 4-chloro-4-deoxy-a-Dgalactopyranos yl -β-D -fructofuranos ide; 4 - chloro -4 -de oxy-ar-D 15 galactopyranosyl-l-chloro-l-deoxy-3-D-fructofuranoside; 4-chloro4-deoxy-n-D-galactopyranosyl-l, 6-dichloro-l, 6-dideoxy-/3-D-fructofuranoside; or 4,6,1', 6’-tetrachloro-4,6,1', 6' -tetradeoxysucrose.

6. A method according to Claim 1, substantially as herein described. 20

7. An ingestibie product or oral composition (as herein defined) containing a compound of the general formula (I) as defined in Claim 1.

8. A product or composition according to Claim 7 containing a compound of the general formula (I) in which R~ represents a chlorine atom,

9. A product or composition according to Claim 7 or Claim 8 5 in the form of a beverage or other liquid also containing an additive to improve mouthfeel,

10. A product or composition according to Claim 9, in which the additive is pectin or a vegetable gum.

11. A product or composition according to Claim 7, substantially 10 as herein described.

12. An ingestible product or oral composition substantially as herein described in any of Examples 7 to 10.

13. A sweetening composition comprising a compound of the general formula (I) as defined in Claim 1 together with a solid extender 15 or carrier, or a liquid extender or carrier containing an adjuvant.

14. A sweetening composition according to Claim 13 containing a compound of formula (I) in which R^ represents a chlorine atom.

15. A composition according to Claim 13 or Claim 14 in the foi·.·. of tablets, granules or a solution in a dropper pack. ¢4757

16. A composition according to any of Claims 13 to 15, substantially as herein described.

17. A sweetening composition, substantially as described in Example 5 or Example 6. 5

18. 1'-chloro-l' -deoxysucrose.

19. 4-chloro-4-deoxy-o;-D-galactopyranosyl-l -chloro-l -deoxyβ-D-f ructofuranoside.

20. 4, 6,1', 6 r -tetrachloro-4, 6,1', 6' -tetradeoxysucrose. Dated this 7th day of January, 1977.