JPS6254796B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 4,1',6'-trichloro-4,1',
Novel 6 of 6'-trideoxygalactosucrose
- Concerning derivatives and their use, especially as sweeteners.

4,1',6'-trichloro-, a powerful sweetener
4,1',6'-trideoxygalactosucrose (designated herein as TGS) is described in GB 1543167 and claims are made for its use. This sweetener has approximately 600 times the sweetening power of sucrose and provides a crisp, pure sweet taste without bitterness or unpleasant aftertaste. The inventors have demonstrated that a new class of non-toxic simple derivatives of TGS surprisingly have very similar sweetening effects and/or can be used as important intermediates in the production of TGS. I found out.

According to the invention, the general formula (wherein X is a hydrogen atom or an alkoxy or arylalkoxy group) is provided.

In particular, compounds of the formula, where X represents a hydrogen atom or a methoxy group, are potent sweeteners, similar in potency to TGS itself. There is therefore also provided a method for sweetening a substance, which consists in mixing into the substance one of the sweetening compounds mentioned above. Also provided are ingestible products or oral compositions or sweetened compositions containing one of the sweetening compounds described above. A process for producing TGS itself is also provided by reacting a compound of the above formula (wherein X represents an alkoxy or aralkoxy group) with an ether cleaving agent.

Other 6-etherified or 6-deoxy sugar derivatives have always been found to have a bitter taste or at least to be significantly less sweet compared to the parent sugar, so that the above TGS derivatives are very It's amazing how sweet it is. For example, Birch and Lee [J.Food Sci. 41 (1976) 1403−
[1407] show that a wide range of sugar ethers, including various 6-etherified sugar derivatives, have a tasteless or bitter taste. however,
The 6-ether of TGS and 6-deoxy TGS have substantially the same degree of sweetness as TGS, and have at least the same degree of stability.

The novel compounds according to the invention include alkyl and aralkyl ethers. Representative alkyl ethers include lower alkyl ethers such as methyl, ethyl, isopropyl or tertiary butyl ether. Representative aralkyl ethers include phenealkyl ethers such as benzyl ether. Methyl ether has particularly good water solubility, taste profile and sweetness (approximately 500 times that of sucrose, compared in a 10% solution),
Particularly interesting as an alternative to TGS. The 6-deoxy form (where X is a hydrogen atom in the formula) is also of particular interest, as it is about 400 times sweeter than sucrose when compared in a 10% solution.

These sweetening compounds can be blended with any substance that requires sweetness.

As used herein, the phrase "ingestible product" means a product that is intended to be swallowed in its normal route of use, such as a food or beverage or a pharmaceutical composition that is administered orally; Includes pre-diluted concentrates. "Oral composition" means a composition that is not intended to be ingested as such in the normal route of use, but is taken into the mouth for the purpose of treating the throat or oral cavity, such as toothpaste, toothpaste, mouth rinse, etc. means a mouthwash, tablet, dental lotion or chewing gum.
The term "sweetened composition" means that it is not taken into the mouth for consumption or retention in the mouth by itself, but is instead added to other ingestible products or oral compositions. means a composition intended to impart sweetness or increase sweetness.

Generally, the sweet derivative according to the invention can be used in the same way as TGS itself. For example, methyl ether (at a 10% dilution) is about 500% as sucrose
The 6-deoxy form is approximately 400 times sweeter than sucrose (at 8% dilution).
Therefore, the amount usually used is about 400 to 500 times less sucrose than the amount of sucrose needed to achieve the desired degree of sweetness.
It is. If desired, further ingredients can be added, such as ingredients that modify the "mouthfeel" of the product.

Sweetened compositions are prepared by mixing the sweetening compound with an excipient or carrier consisting of a suitable vehicle for the purpose of formulating a convenient product such as a granule, tablet or infusion solution. Can be done. Bulking agents or carriers include the usual water-dispersible tablet ingredients such as starch, lactose and sucrose, e.g. spray-dried maltodextrin, and auxiliary agents such as stabilizers, colorants and viscosity modifiers. There is an aqueous solution.

Beverages such as soft drinks containing ether derivatives can be manufactured either as sugar-free diet products or as "reduced sugar" products containing the minimum amount of sugar required by law. The present invention also includes within its scope dilutable concentrates, such as bottled syrups, fruit squash, and instant desserts.

The ether compounds according to the invention can be prepared by the action of a suitable etherification agent on TGS, which can optionally be 2,3,3' and
Either of the 4' positions can be protected from etherification. A convenient etherification agent for obtaining methyl ether is diazomethane, customarily used in the presence of a Lewis acid such as boron trifluoride. Other etherification agents include alkyl and aralkyl halides (eg methyl iodide-Padey's reagent used with silver oxide) and sulfates (eg dimethyl sulfate in alkaline medium) and benzyl trichloroacetimidate. Hydroxyl groups in the 2, 3, 3' and 4' positions can be protected by convenient methods such as acetylation and esterification. 2,3-acetals together with 6-hemiacetals, e.g.
It is particularly advantageous to form an -O-isopropylidene derivative and then esterify it.
Under moderate conditions (eg, acetic anhydride/pyridine, room temperature), the hydroxyl group at position 6 remains unesterified and the hemiacetal is removed during processing.
The protecting group can be removed after etherification.

Furthermore, from the corresponding 4,6-O-benzylidene or 4,6-O-isopropylidene derivatives of sucrose esterified at the 1', 2, 3, 3', 4' and 6' positions, benzyl and isopropylether can be obtained. These are known compounds (Khan, Carbohydrate Research 1974,
32 , 375; Khan, Mufti and Jenner, ibid. 1978,
65 , 109). These can be treated with a hot hydride-type reducing agent, such as an alkali metal cyanoborohydride, to produce the corresponding 6-benzyl or 6-isopropyl ether hexaesters, which can be deesterified to form the 6-ether of sucrose. can be generated. By a method analogous to the chlorination of sucrose 6-ester (see UK Patent Application No. 2079749A), this 6-ether is reacted with a chlorinating agent selectively at the 4, 1' and 6' positions. Can be chlorinated. Preferred chlorinating agents are Vilsmeyer-type reagents for ease of use and selectivity, i.e., having the general formula (XClC=NR ₂ )Cl ^- (wherein R represents a methyl or ethyl group and
represents a hydrogen atom or a methyl group)
N-dialkyl (chloromethaniminium).

Another chlorinating agent that can be used is sulfuryl chloride, which reacts to form the chlorosulfate of the initially available hydroxyl group. These chlorosulfates are then or simultaneously decomposed to invert the configuration and provide the corresponding chlorodeoxy derivatives. Conveniently, the chlorosulfated intermediate can be isolated, for example, by pouring the reaction mixture into an ice-cold sulfuric acid solution and extracting the acid with a solvent such as chloroform. The product obtained can be dechlorosulfated in conventional manner, for example by treatment with a catalytic amount of an iodide, such as sodium iodide, preferably in the cold. However, sulfuryl chloride is less selective than the Vilsmimer reagent, so the latter is preferred.

Also, 4,6-O-benzylidene or 4,6
The 4-hydroxy-6-ether hexaester obtained by reductive decomposition of the -O-isopropylidene derivative is chlorinated at the free 4-position, de-esterified, and then further chlorinated at the 1' and 6' positions. can be converted into The triphenylphosphine/carbon tetrachloride reagent is highly suitable for this purpose.

The 6-alkyl and aralkyl ethers of TGS can be used as important intermediates for producing TGS itself. Therefore, reaction with an ether cleaving agent yields TGS. A particularly easy reaction involves 6-benzyl ether,
This can be hydrogenated using a catalyst system (Raney Nickel) to remove the benzyl group to produce the 6-hydroxy product. Other ether cleavage agents include mild acid reflux, e.g.
There are inorganic acids such as hydrochloric acid at 1N concentration.

6-deoxyTGS (formula, X is H)
can be obtained by debromination of 6-bromo TGS, for example by treatment with Raney nickel in the presence of hydrazine hydrate.

The following examples further illustrate the invention.

Example 1 6-O-methyl TGS: 1,6-dichloro-
1,6-dideoxy-β-D-fructofuranosyl-4-chloro-4-deoxy-6-O-methyl-α-D-galactopyranose (a) Acetalization of TGS TGS (18 g) was dissolved in dry dimethylformamide. (200ml) was treated with 2-methoxypropene (18ml) for 3 hours at 70°C in the presence of p-toluenesulfonic acid (80mg). By TLC (ethyl acetate/acetone/water 6:8:1),
Several products were seen, indicating that starting material was running out. The reaction was then cooled and mixed with pyridine (100ml) and acetic anhydride (75ml).
ml) at room temperature for 18 hours. TLC (ether/volatile oil 7:1) showed four products. The reaction mixture was concentrated to half volume and then poured into ice/water. The precipitate was separated, washed with water, dissolved in ether, dried (sodium sulfate), and eluted from the silica gel column with ether-volatile oil (1:1) to give the 3',4'-di- O-acetyl-4・
1',6'-trichloro-4,1',6'-trideoxy-2,3-O-isopropylidene galactosucrose (10 g, yield 40%) was produced. The structure was confirmed by ¹ H-nmr and mass spectrometry analysis.

(b) Methylation A solution of the product (4 g) of step (a) in dichloromethane (40 ml) was cooled to 0°C, treated with a freshly prepared dichloromethane solution (10 ml) of diazomethane, and then 1 drop of diazomethane was dissolved in dichloromethane (40 ml). Boron trifluoride-diethyl ether complex was added, followed by a further addition of diazomethane in dichloromethane (15 ml). TLC (ethyl acetate/volatile oil 2:3)
indicated that a single major product was formed. The reaction was filtered and the filtrate was washed with 10% sodium bicarbonate solution and water, then dried (sodium sulfate) and concentrated to a syrup. This product was eluted from a silica gel column using ethyl acetate-volatile oil (1:3), resulting in 3'.
4'-di-O-acetyl-4,1',6'-trilichloro-4,1',6'-trideoxy-2,3-O
-isopropylidene-6-O-methylgalactosucrose (3.5 g, 83%) was obtained.

(c) Deprotection A solution of the product (3.5 g) in step (b) in acetic acid (15 ml) was treated with water at 70°C for 10 minutes. The reactant,
It was concentrated by azeotroping with toluene, and the resulting syrup was taken up with methanol and treated with a catalytic amount of sodium methoxide for 5 hours at room temperature. The solution was deionized by shaking with a resin layer (CO ₃ ^2- form) mixed with Biodeminrolit, concentrated to a syrup, and eluted from a silica gel column using ethyl acetate-acetone (1:1). , 6-O-methyl-TGS
(1.9g, 71%). [α] _D +76.4° (c1.0, methanol).

Analysis Calculated value for C ₁₃ H ₂₁ O ₈ Cl ₃ C, 37.9; H, 5.10; Cl, 25.9 Actual value C, 39.5; H, 5.69; Cl, 22.4 The structure of 6-O-methyl-TGS is ¹³ C −nmr
This was confirmed by mass spectrometry.

¹ H-nmr data (200MHz): 5.69 (d, J ₁ , ₂
3.0Hz, H-1), 4.12 (dd, J ₂ , ₃ 9.4Hz, H
-2), 4.24 (m, J ₃ , ₄ 1.6Hz, H-3),
4.56 (m, H-4), 5.68 (t, J _{3 '} , 4'6.8
Hz, H-3'), 5.44 (t, _J4 ', ₅ 6.8Hz, H-
4'), 3.40 (s, OMe), 2.09 (s, OAc),
1.42 (s, Me), 1.47 (s, Me) ¹³ C-nmr data: ppm 104.8 (C-2'); 94.1
(C-1); 82.6 (C-5'); 77.6 (C-
3'); 77.0 (C-4'); 74.0 (C-5);
70.4 (C-6); 69.4/69.0 (C-2/C-
3); 64.8 (C-4); 60.2 (OCH ₃ ); 46.2
(C-1'); 45.1 (C-6'), mass spectrum [(a) shows hexopyranosyl cation containing 1Cl (3:1 doublet), (b) shows
Indicates a ketofuranosyl cation containing 2Cl (9:6:1 triplet)]: m/e283(a), 235(a), 223
(b), 193(a), 177(a).

Example 2 6-O-isopropyl TGS: 1,6-dichloro-1,6-dideoxy-β-D-fructofuranosyl 4-chloro-4-deoxy-6-O-
Isopropyl-α-D-galactopyranose (a) Reductive cleavage of 4,6-isopropylidene sucrose hexaacetate ring A solution of 4,6-isopropylidene sucrose hexaacetate (5 g) in THF (50 ml) was added with a molecular sieve. After adding Form 3A (5 g) and sodium cyanoborohydride (5 g), the stirred reaction mixture was cooled to 0° C. using an ice bath/salt bath. The reaction mixture was acidified with HCl in ether until boiling ceased. The process of the reaction is described above to make it acidic.
TLC (ethyl acetate:acetone:water 6:8:
1), it was found that the reaction was completed in 45 minutes.

The reaction mixture was poured into methylene chloride,
Washed three times with a saturated solution _{of NaHCO3} , then water, dried over _Na2SO4 , filtered, and the filtrate was concentrated and chromatographed on a silica gel column. Ether - petroleum ether (3:
1), pure 4-hydroxy-6
-Produced isopropyl sucrose hexaacetate (4.69 g; 94.5%). nmr shows a −OH peak, which fits the structure. Literature:
Garegg.Huttberg and Oscarson; J.Chem.Soc.
Perkin1, 1982, 2395.

nmr (CDCl ₃ ): τ4.38 (d, 1H, J ₁ , ₂ 3.5
Hz, H-1), 5.19 (q, 1H, J ₂ , ₃ 10Hz,
H-2), 4.61 (t, 1H, J ₃ , ₄ 9.5Hz, H-
3), 5.62 (q, 1H, J ₄ , ₅ 10Hz, H-4),
4.54 (d, 1H, _J3 ', _4'6Hz , H-3'), 4.6
(t, 1H, _J4 ', _5'6.5Hz , H-4'), 7.8-7.92
(m, 18H, C ₁₂ H ₁₈ ), 8.8 (s, 3H, CH ₃ ),
8.84 (s, 3H, CH ₃ ), 8.14 (s, 1H,
OH).

(b) 4-chloro-6-O-isopropyl-galactosucrose hexaacetate triphenylphosphine (6.1 g) was added to the step
A solution of 4-OH-6-isopropyl-sucrose hexaacetate (5 g) obtained from (a) in pyridine (50 ml) was added to the cooled mixture (10°C). After 15 minutes add carbon tetrachloride (1.6 ml) to the reaction mixture.
added. After 10 minutes, the reaction mixture was removed from the ice bath, allowed to cool to room temperature, and left at this temperature for 1 hour. It was then transferred to a preheated oil bath at 80° C. for 2 hours. TLC (ether) showed one fast moving product. The reaction mixture is
After adding methanol, it was concentrated to a syrupy state. This was eluted from a silica gel column using ether:petroleum ether (3:1) to yield the title compound (4.8 g, 95%). nmr (CDCl ₃ ): τ4.26 (d, 1H, J ₁ , ₂
3.5Hz, H-1), 4.74(q, 1H, J ₂ , ₃ 10Hz,
H-2), 4.64 (q, 1H, J ₃ , ₄ 3.5Hz, H-
3), 5.34 (q, 1H, J ₄ , ₅ 2Hz, H-4),
4.5 (d, 1H, _J3 ', _4'65Hz , H-3), 4.55
(t, 1H, _J4 ', _5'6.5Hz , H-4'), 7.82-7.88
(m, 18H, C ₁₂ H ₁₈ ), 8.82 (s, 3H, CH ₃ ),
8.84 (s, 3H, _CH3 ).

(c) 4-Chloro-6-O-isopropylgalactosucrose 4-chloro-6-O-isopropylsucrose hexaacetate in AR methanol (30ml)
Sodium methoxide (1N) was added to the solution to adjust the pH of the solution to about 9. The reaction mixture was left at room temperature for several hours. TLC (ethyl acetate:acetone:water; 6:8:1) showed a single product. After the reaction mixture was neutralized with IR15H ⁺ type resin, the resin was quickly removed by filtration. It is important to keep the reaction mixture alkaline or neutral, as the presence of acid during concentration can break the glycoxide bonds. The filtrate was concentrated and dried in vacuo to yield the title compound (1.7 g, 97%).

(d) 6-O-isopropyl TGS: triphenylphosphine (3.9 g), 4-
A cold solution of chloro-6-O-isopropylgalactosucrose (1.5 g) in pyridine (20 ml) (0
℃). After approximately 10 minutes, carbon tetrachloride (1.3 ml) was added to the cold solution. After approximately 15 minutes, the reaction mixture was removed from the ice bath and allowed to warm to room temperature. After being left at room temperature for about 1.5 hours, it was heated at 70°C for 16 hours. TLC (ethyl acetate:acetone:
water; 6:8:1) than TGS, with a fast-moving main product, some slow and fast by-products,
and showed about 10% starting material. After adding methanol, the reaction mixture was concentrated to a syrup. When ether is added, most by-products based on triphenylphosphine precipitate out;
It was filtered. The filtrate was concentrated again and eluted from the silica gel column with ethyl acetate:acetone; 3:1 to yield 6-isopropyl TGS (1.06
g; 65%). The product was fully acetylated (pyridine/acetic anhydride) and the nmr spectrum was taken.

nmr (CDCl ₃ ): τ4.34 (d, 1H, J ₁ , ₂ 3.0
Hz, H-1), 4.7 (2H, H-2 and H-3),
5.36 (m, 1H, H-4), 4.3 (d, 1H, J ₃
′, ₄ ′6.5Hz, H-3′), 4.55(t, 1H, J ₄ ′, ₅
'6.5Hz, H-4'), 7.84-7.9 (m, 12H,
C ₈ H ₁₂ ), 8.84 (s, 3H, CH ₃ ), 8.88 (s,
3H, _CH3 ).

Example 3 4,1',6'-trichloro-4,6,1',6'-tetradeoxygalactosucrose (6-deoxyTGS) (a) 6-bromo-4,1',6'-trichloro- 4.
6,1',6'-tetradeoxygalactosucrose tetraacetate 2,3,3',4'-tetra-O-acetyl-
A solution of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose (6 g) in pyridine (60 ml), triphenylphosphine (6.12 g) and carbon tetrachloride (3.9 g) The mixture was initially treated at 0°C for 1 hour and then at 65°C for 3 hours. TLC (ether: petroleum ether; 4:
1) indicated the presence of one fast moving product. After adding methanol (25 ml) to the reaction mixture, it was concentrated to a syrupy state. Elution of the syrup from a silica gel column with ether:petroleum ether (2:1) produced the 6-bromo derivative, which crystallized from the ether/petroleum ether.

(b) 4,1',6'-trichloro-4,1',6,6'-
Tetradeoxygalactosucrose A solution of the product from step (a) (1 g) in methanol was refluxed with Raney nickel in the presence of barium carbonate (1 g). When reflux began, hydrazine hydrate (1 ml) was added to the mixture. After 10 minutes, an additional 1 ml of hydrazine hydrate was added through the condenser. After 30 minutes, the reaction mixture was filtered through filter aid, then concentrated to a syrup and eluted from a small silica gel column with 1% aqueous ethyl acetate to produce 6-deoxy TGS. [α] _D +
87.1° (c1.0, acetone); ¹³ C-NMR spectrum (D ₂ O solution, relative value with internal standard DSS as 0 ppm) Carbon atom chemical shift, ppm 2' 106.02 1 95.41 5' 83.75 3' 78.89 4 ′ 78.04 5 70.95 4 70.03 2 69.78 3 69.28 1′ 47.46 6′ 45.99 6 19.61 4・1′・6′-Trichloro-4・6・1′・6′-tetradeoxygalactosucrose is sucrose (8% solution) It was found to have a sweetness that is 400 times sweeter.

Example 4 6-O-benzyl TGS: 1,6-dichloro-
1,6-deoxy-β-D-fructofuranosyl 4-chloro-4-deoxy-6-O-benzyl-α-D-galactopyranoside (a) 1', 2, 3, 3', 4 ',6'-Hexa-O-acetyl-6-O-benzyl sucrose (1) Molecular sieve powder type 3A (10 g) was added to a THF (100 ml) solution of 4,6-benzylidenesucrose hexaacetate (10 g). Added. The reaction mixture was cooled to 0°C and added with sodium cyanoborohydride (NaCNBH ₃ ) (15
g) was added. After about 10 minutes, the reaction mixture was diluted with diethyl ether and hydrochloric acid.
Acidification was continued until HCl gas evolution ceased. The reaction was observed by TLC (ether). After about 1 hour about 50% product had formed. At this stage, more acidified ether was added and the reaction mixture was stirred for a further 1 hour. TCL as the main product
(1) (90%), and showed some slow or fast products. The reaction mixture was diluted with dichloromethane (200ml) and water and filtered through Celite.
The organic layer was separated, dried over sodium sulfate, and concentrated to a syrup. syrup,
Elution from the silica gel column with ether:petroleum ether (2:1) gave 9 g (90% yield) of (1).

(b) 6-O-Benzylsucrose (2) 1 (5 g) in methanol (10 ml) was treated with a catalytic amount of sodium methoxide for 4 hours at room temperature to give Amberlyst 15 (H ⁺ ) (registered trademark). 2 (3 g, 95%)
was generated.

(c) 6-O-benzyl-4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose (3) A solution of 2 [2 g, in DMF (10 ml)] was added to Vilsmeier. using reagents (detailed method described in GB 2079749) (prepared from DMF and PCl ₅ ), initially at 0°C for 20 minutes and then
It was treated at 120°C for 8 hours. The reaction mixture was cooled to 20°C and diluted with methanol-ammonium hydroxide (2:
1, ml) was added and the temperature was maintained below 50°C. The solution was concentrated and purified on a small silica gel column [using ethyl acetate:acetone (1:1)] to give 3 (0.67 g, 30%), mp55-
57°C; [α] _D +5.8° was generated.

Mass spectral data [Ions marked (a) are hexapyranosyl (“galacto”) cations; ions marked (b) are ketofuranosyl cations].

M/e271a, 199b, 180a, 163b, 144a, 127b Example 5 Production of TGS from 6-benzyl ether (a) 6-O-benzyl-4・1′・6′-trichloro-4・1′・6′ -trideoxygalactosucrose tetraacetate (4) The product of Example 4 was treated in a conventional manner with acetic anhydride (2 ml) and pyridine (5 ml) at room temperature for 6 hours, resulting in 4 (0.68 g, 100%).

(b) Dissolve a sample of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose (5) 4 (500 mg) in methanol (10 ml), with a spatula). To this reaction mixture was added 1.5 ml of hydrazine hydrate. The mixture was then stirred at room temperature for 8 hours. TCL
[Ethyl acetate:acetone:water (6:8:1)]
showed one major product and one rapidly fluctuating side product. The catalyst was filtered off and the reaction mixture was concentrated and loaded onto a silica gel column. Elution using ethyl acetate:acetone (1:1) as a solvent produced TGS (5). (0.27g, 65%), which was the same as the standard sample.

Example 6 6-O by benzylation of perchlorinated raw material
-Benzyl TGS (a) 4,1',6'-trichloro-4,1',6'-trideoxy-6-O-tritylgalactosucrose (6) A solution of TGS (20 g) in pyridine (200 ml),
It was treated with trityl chloride (28g) at 80°C for 1 hour. The reaction mixture was concentrated, taken up in dichloromethane, washed successively with water, aqueous sodium bicarbonate and water, and dried over sodium sulfate. The solution was concentrated and eluted from a silica gel column with diethyl ether to give 6-(25 g,
77%).

Conventional acetylation of 6 (10 g) with acetic anhydride (15 ml) and pyridine (100 ml) at room temperature for 6 hours yielded the peracetylated derivative 7 (12 g,
95%).

(b) 2,3,3',4'-tetra-O-acetyl-
A solution of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose (8) 7 (11 g) in 60% acetic acid aqueous solution (150 ml) was heated at 90°C for 15 minutes. . TLC
[Ether-volatile oil (4:1)] showed a slow moving product. Concentrate the solution to ether
Elution from a small silica gel column with volatile oil (2:1) gave 8 (6.92 g, 90%).

(c) 6-O-benzyl-4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose tetraacetate (4) A dichloromethane solution of 8 (5.0 g) was dissolved in excess benzyl trichloro. 60 using imidate
It was treated at ℃ for 6 hours. The reaction mixture was concentrated and eluted from a silica gel column with ether-volatile oil (2:1) to yield 4 (1.7 g, 30%).
was generated.

(d) Treatment of 4 with a catalytic amount of sodium methoxide in dry methanol produced the same 6-O-benzyl TGS as the product of Example 4.

Example 7 Production of TGS from 6-O-isopropyl-TGS 10 ml of 6-O-isopropyl TGS (1.0 g)
of 1N hydrochloric acid and the solution on a water bath for approximately 50 min.
Warmed at ℃ for several hours. The reaction mixture was then cooled, neutralized with sodium carbonate and evaporated to dryness in vacuo. The residue is then chromatographed on silica gel to give a pure
Generated TGS.

In the example below, the methyl ether of TGS is
It is expressed as MTGS, and the 6-deoxy form is expressed as DTGS.

Example 8 Sweetened Tablets for Beverage Each tablet was prepared with a dispersible tablet base (approximately 60 mg) containing sucrose, gum arabic, and magnesium stearate, along with MTGS
(8mg) or DTGS (10ml), approximately 4.5g
is equal to the sweetness of sucrose.

Example 9 Bulk Sweetener A bulk sweetener having the same taste as an equal volume of sucrose (granulated sugar) is prepared by mixing the following ingredients and spray drying to a bulk density of 0.29 ml ^-1 .

Maltodextrin solution 22.2 g (dry weight) MTGS 2.0 g or DTGS 2.5 g The resulting composition has a sweetening power equal to approximately 2 Kg of sugar.

Example 10 Low calorie cola drinks containing sugar Ingredients for the manufacture of 100ml bottled syrup MTGS 80mg or DTGS 100mg 60g sugar Benzoic acid 35g (Concentrated) phosphoric acid 1ml Cola flavor 1.1ml Coloring agent appropriate amount Bring the total volume to 100ml with mineral water.

This syrup can then be added in an amount of 25 ml to each 225 ml of chilled carbonated mineral water.

Example 11 Carbonated low calorie lemonade (unsweetened) Ingredients to make 100ml syrup: MTGS 100mg or DTGS 125mg Benzoic acid 35mg Citric acid (dry basis) 1.67g Lemon essence 0.8g Bring the total volume to 100ml with mineral water.

This syrup can be added in doses of 25 ml to 225 ml of chilled carbonated mineral water.

Example 12 Altered Toothpaste Weight % Calcium Hydrogen Phosphate 50 Glycerin 20 Sodium Lauryl Sulfate 2.5 Spearmint Oil 2.5 Gum Tragacanth 1.0 MTGS 0.03 Water 23.97 Ingredients were mixed to create a spearmint flavor with acceptable sweetness but no sugar or saccharin. Generate alchemy toothpaste with.

Example 13 Chewing Gum Parts by Weight Polyvinyl Acetate 20 Butylphthalyl Butyl Glycolate 3 Polyisobutylene 3 Microcrystalline Wax 3 Calcium Carbonate 2 Flavor/Aroma 1 MTGS 0.07 or DTGS 0.09 Glucose 10 The above chewing gum base can be prepared in the form of conventional tablets or strips. It can be cut into.

Claims (1)

[Claims] 1. General formula (wherein, X represents a hydrogen atom, an alkoxy group, or an arylalkoxy group). 2. The compound according to claim 1, wherein X is a methoxy group or a hydrogen atom. 3. The compound according to claim 1, wherein X is a benzyloxy group or an isopropoxy group. 4 Sweetener is a general formula (In the formula, X is a hydrogen atom or a methoxy group)
A sweetening composition containing a sweetener mixed with an additive or carrier. 5 General formula (wherein X represents an alkoxy or arylalkoxy group) is reacted with an ether cleaving agent. Method for producing galactosucrose. 6. The method according to claim 5, wherein X represents a benzyloxy group and the reagent is catalytic hydrogen.