JPS5973596A - Sucrose derivative - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 4,1', 6'-)lichloro-4,1'
.

The present invention relates to new 6-derivatives of 6'-trideoxygalactosucrose and their uses, especially as sweeteners.

The potent sweetener 4,1',6'-)lychloro-4,1',6'-)lysoxygalactosucrose (designated herein as TGS) is described in British Patent No. 1,543,167. This sweetener has approximately 600 times the sweetening power of sucrose and provides a light, pure sweetness without bitterness or unpleasant aftertaste. The inventors are T
It has now been found that new, relatively non-toxic, simple derivatives of GS surprisingly have very similar 1f taste-adding effects and/or can be used as important intermediates in the production of 1dTG8.

According to the present invention, there is provided a compound of the general formula: or a hydrogen atom or an alkoxy or arylalkoxy group.

In particular, the compounds of formula I, where X represents a hydrogen atom or a methoxy group, are potent sweeteners with a strength of T
Similar to GS itself. There is therefore also provided a method for sweetening a substance, which consists in mixing one of the sweetening compounds mentioned above into the substance. 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 the above-mentioned compound 2 (with the proviso that it 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 TG8 derivatives mentioned above are very For example, Birch and Lee [, r,
Food sci, 41 (1976) 1403-
1407), a wide range of sugar ethers are
- indicates that it has a tasteless or bitter taste, including etherified sugar derivatives.

However, the 6-ether of T()8 and 6-deoxy TG8 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. Typical alkyl ethers are
Includes lower alkyl ethers such as methyl, ethyl, isopropyl or tertiary butyl ether. Typical aralkyl ethers include benzyl ether
There is an alkyl ether. Methyl ether has particularly good water solubility, taste profile and sweetness (approximately 500 times that of Sukup-su, compared with 10% solution) and has a T
Particularly interesting as a replacement for GS. The 6-deoxy form (formula I when X is a hydrogen atom) is also of particular interest;
When compared with a 10% solution, it is approximately 400 times sweeter than sucrose.

These sweetening compounds can be incorporated into any substance that requires sweetness.

As used herein, the phrase "consumable product" means
Refers to products intended to be swallowed in the normal route of use, such as foods or beverages or pharmaceutical compositions for oral administration, and includes concentrates that are diluted before use. "Oral compositions" are
Compositions that are not intended to be ingested but are taken into the mouth for the purpose of treating the throat or oral cavity, such as toothpastes, toothpastes, mouthwashes, mouth rinses, tablets, dental lotions or chewing gum. means.

The term "sweetened composition" does not by itself be taken during the day for consumption or retention during the day, but instead includes other ingestible products or oral compositions. A composition intended to impart sweetness or increase sweetness by adding it to.

Generally, the sweet derivative according to the invention can be used in the same way as TGS itself. For example, methyl ether is (1
In 0% dilution, it is about 500 times sweeter than sucrose, and the 6-deoxy form is about 400 times sweeter than sucrose (in 8% dilution). Therefore, the amount normally used is about 40% of the sucrose needed to achieve the desired sweetness level.
00 to 1/500. If desired, further ingredients can be added, such as ingredients that modify the "mouthfeel" of the product.

Sweetened compositions can be 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 pack solution. . 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 that

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

The ether compounds according to the invention can be prepared by the action of a suitable etherification agent on TGS,
S can be protected from etherification at any of the 2,3,3' and 4' positions if desired. A convenient etherification agent for obtaining methyl ether is sia ψmethane, customarily used in the presence of a Lewis acid such as boron trifluoride.

Other etherification agents include argyl and aralkyl halides (eg methyl iodide-Padi's reagent used with silver oxide) and sulfates (eg dimethyl sulfate in alkaline medium) and benzyl trichloroacetimidate. 2.6. Hydroxyl groups in the 3' and 4' positions can be protected by convenient methods such as acetylation and esterification. 2,6-acetals together with 6-hemiacetals, e.g. 2.3-0
It is particularly advantageous to form the -impropylidene 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.

Also, from the corresponding 4,6-0-benzylidene or 4,6-0-isopropylidene derivatives of sucrose esterified at the 1', 2, 6, 3', 4' and 6' positions,
Pencil and inpropyl ether can be obtained. These are known compounds (Khan, Oar
'bohydrate Re5earch1974.3
2 j375 i Khan, Mu, fti and Jen
ner, 1978, 65, 109) o these,
Treatment with a mild hydride-type reducing agent, such as an alkali metal cyanoporohydride, can produce the corresponding 6-benzyl or 6-impropyl ether hexaesters, which can be deesterified to give the 6-ether of sucrose. can be generated. By a method analogous to the chlorination of sucrose 6-ester (see GB Patent Application No. 2.079,749A), this 6-ether is reacted with a chlorinating agent to form the 4.1' and 6' positions. It can be selectively salted. Preferred chlorinating agents are Vilsmeier-type reagents from the viewpoint of ease of use and selectivity, i.e., those having the general formula %, where R represents a methyl or ethyl group, and X represents a hydrogen atom or a methyl group. N chloride.

Another chlorinating agent that can be used is sulfuryl chloride, which reacts to form a chlorosulfate of the initially available hydroxyl group.

These chlorosulfate esters 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 a water-cooled 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 Vilsmeier's reagent, so the latter is preferred.

In addition, after chlorinating the free 4-position and deesterifying the 4-hydroxy-6-ether hexaester obtained by reducing the 4,6-0-benzylidene or 4,6-0-impropylidene derivative, , 1' and 6' positions can be further chlorinated. The triphenylphosphine/carbon tetrachloride reagent is very suitable for this purpose.

The 6-alkyl and aralkyl ethers of TGS are
It can be used as an important intermediate for producing TGS itself. Therefore, reaction with an ether cleaving agent yields TGS. A particularly facile reaction involves the 6-benzyl ether, which can be hydrogenated using a catalyst system (Raney nickel) to remove the benzyl group to form the 6-hydroxyProxy product. Other ether cleavage agents include a mild acid environment, e.g.
There are inorganic acids such as N-concentrated hydrochloric acid.

6-Deoxy TGS (formula 1, X is H) can be obtained by desolomization of 6-bromo TGS, for example by treatment with Raney nickel in the presence of hydrazine.

The following examples further illustrate the invention.

Example 1 6-0-methyl TGS: 1,6-dichloro-1,6-sideoxy-β-D-fructofuranosyl-4-chloro-4-deoxy-6-o-
Methyl-α-D-galactopyranose (a) TGS acetalization TGs (18,9) was dried in dimethylformamide (20
The solution in 0 m/) was treated with 2-methoxypropene (18-) for 3 hours at 70°C in the presence of I)-) luenesulfonic acid (80 μl). With TI,C (ethyl acetate/acetone/water 6:8:1) several products were seen,
It became clear that the starting material was missing. The reaction was then cooled and treated with pyridine (100-) and acetic anhydride (75-) at room temperature for 18 hours. In TLO (ether/volatile oil 7:1) four products were seen.

The reaction mixture was concentrated to half volume and then poured into ice/water. The precipitate was filtered off, washed with water, dissolved in ether, dried (sodium sulfate), and eluted from the silica sol column with ether-volatile oil (1:1) to give 3/, 41-di-acetate. 4, I',
6'-trichloro-4,1'.

6'-trideoxy-2,3-0-isozolobylidene galactosucrose (10,9, yield 40%) was produced. The structure was confirmed by H-nmr and mass spectrometry analysis.

(b) The product (4 g) of the methylation step (a) was added to dichloromethane (40 m
e) was cooled to 0 °C and treated with a freshly prepared solution of shea-domethane in dichloromethane (10, d), after which one drop of boron trifluoride-diethyl ether complex was added, A further solution of diazomethane in dichloromethane (15 td) was then added. 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).
, concentrated to syrup. The product was eluted from a silica sol column with ethyl acetate-volatile oil (1:3) to yield 5Z 4'-diO-acetyl4,
1',6'-Trichloro-4,1',6'-trideoxy-2,3-0-impropylidene-6-0-methyl lactosucrose (3.5 g, 83 t) was obtained.

(c) A solution of the product (3,!M) of the deretention step (b) in acetic acid (15 m/) was treated with water at 70°C for 10 minutes. The reaction was concentrated by azeotroping with toluene and the resulting syrup was taken up in methanol and treated with a catalytic amount of sodium methoxide for 5 hours at room temperature. The solution was heated to 1310 (
6-0- Methyl-'I'
G8 (section 1, 99, 71) was generated. 〔α〕ゎ＋
76.40 (01,0, methanol).

Calculated value for analysis 013H2108C"3 0.37.9; H, 5, 10; C
E, 25.9 Actual value 0,39.5; H, 5,69; c
The structure of i, 2 2.4 6-0-methyl-TGS is 130-nm r
This was confirmed by mass spectrometry analysis.

”H-nmr data (200MHz): 5.69
(d, Jl, 23.0Hz, H-1), 4.12
(dd, J2, 39.411z.

H-2), 4.24 (m, J3, 41.6Hz j
H-3), 4.56 (m, H-4), 5-68 (t-
J3', 4' 6.8 fiz.

H-3'), 5-44 (tm J4', 56.8Hz
, H-4'), 3.40 (s, oMe), 2
．． 09 (8, OAC), 1.42 (81Mθ), 1.
47 (8,M13)13a-nmr data: ppm
104.8 (c-2'); 94.1 (c-1
); 82.6 (C-5'); 77.6 (a-3'); 7
7.0 (0-4'); 74.0 (0-5); 70.4
(c-6) ; 69.4/ 69.0 (c-2/
C-3); 64.8 ('0-4); 60.2
(0OH3); 46.2 (0-1')? 45.1
(0-6'), mass spectrum [(a) i-j I
CL (ro: indicates a hexopyranosyl cation containing double line), (b) indicates a ketofuranosyl cation containing 2C'-(9:6:1 triple line)): m/8283
(A), 235 (A), C 23 (B), 193
(b), 177 (b).

Example 2 6-0-isopropyl TGS: 1,6-dichloro-1,6-sideoxy-β-D-fructofuranosyl 4
-Chloro-4-deoxy-6-0-isozologyl α-
TH of Kugalactopyranose 4.6-Ituproviridensucrosehegisaacetate (5I)? After adding Molecular Sheep type 6A (5 g) and sodium cyanolobidride (5 g) to the (50 ml) solution, the stirred reaction mixture was cooled to 0° C. using an ice/salt bath. The reaction mixture was acidified with HCL in ether until boiling ceased. Before acidification, the progress of the reaction was followed by TLO (ethyl acetate:acetone:water 6:8:1) and it was found that the reaction was completed in 45 minutes.

The reaction mixture was poured into methylene chloride and diluted with NaHCO2.
Washed 6 times with a saturated bath solution of N a 2
Dry over SO4, filter, concentrate the filtrate and chromatograph on a silica sol column. Elution with ether-petroleum ether (3:1) produced pure 4-hydroxy-6-isoprobyl sucrose hexaacetate (4.69 g 194.5%). nmr is-
oHf-re is shown and is compatible with the structure. Literature: G
arθgg.

Huttberg and 0scarson; J, Oh
em, Soc, perkinl, 1982.23
95゜nmr (0DCJ3): τ4.38 (d, I
H, Jl, 26.5Hz, H-1), 5.19 (CL,
IH, J2, 310Hzm H-2) a 4.61
(tr I Hr J3, 49-5Hz*H-ro),
5.62 (q, I H, J4,510) (z, H
-4).

4-54 (d, I H, J3', 4' 6Hz, H
-3'), 4-6 (t, I H, J4', 5' 6.
5Hz, H-4'), 7.8-7-92(m*
18 H, 0,2H1B) m 8.8 (e, 3
H* cHs) m8.84 (θ-3H# C”H3)
lB, 14 (Ii+, 1H, 0H) 0 (b) 4-
Chloro-6-isozorobyl-galactosucrose hexaacetate triphenylphosphine (6.1 g)'r, step (a)
A solution of 4-OH-6-inzolovyl-sucrose hexaacetate (5 g) obtained from 6m) was added.

After 10 minutes, the reaction mixture was removed from the water bath, allowed to cool to room temperature, and left at this temperature for 1 hour. Then 80°C
and transferred to a preheated oil bath for 2 hours.

TIJO (ether) showed one fast moving product. The reaction mixture was concentrated to a syrup after addition of methanol, which was eluted from a silica sol column using (ether dipetroleum ether i 3:1) to yield the title compound (4.8 g, 95 t). . nm
r ((3DCJ5) :τ4.26(do IHm
Jl, 23.5Hzs H-1)s4.74(CL
II H, J2, 310Hz-H-2) -4-64(
(111HIJ3,4 6.5Hz, H-6),
5.34 ((L, I H2J4.52Hz, H-
4), 4-5 (d.

I Hm J3', 4' 65Hz, H-3), 4
．． 55 (t, IH.

J4', 5' 6.5Hz, H-4'), 7.8
2-7.88 (m.

18 Hm C1zHxa) m B-82('s 3
H# 0H3) *8.84 (s, 3H, 0H
3).

(c) 4-chloro-6-isozorogyl is added to lactosucrose 4-10-6-isopropylsucrose hexaacetate dissolved in AR methanol (30 mA),
Sodium methoxide (1N) was added to bring the pH of the solution to about 9. The reaction mixture was left at room temperature for several hours. T.L.O.
(Ethyl acetate:acetone:water; 6:8:1) showed a single product.After the reaction mixture was neutralized with engineering R15H+ type resin, the resin was immediately removed by filtration. The presence of acids during concentration can break glycosidic bonds, so it is important to keep the reaction mixture alkaline or neutral. The filtrate was concentrated and dried in vacuo to yield the title compound (1.7 g, 97%).

) 6-Inzorogyl TGS Nitriphenylphosphine (3,9g) f,,4-chloro-6-isoprobyl galactosucrose (1,5g)
of pyridine (20m) was added to a cold solution (06C). Approximately 1
After 0 min, carbon tetrachloride (1,000 ml) was added to the cold solution. After about 15 min, the reaction mixture was removed from the water bath and allowed to warm to room temperature. It was left at room temperature for about 1.5 h. rear,
Heated at 70°C for 16 hours. Tll0 (ethyl acetate:acetone:water; 6:8:1) showed a faster moving main product, some slower and faster side products, and about 10 times more starting material than TG8. After adding methanol, the reaction mixture was concentrated to a syrup. Upon addition of ether, most of the by-products based on triphenylphosphine precipitated out and were filtered off. The filtrate was concentrated again and washed off the silica gel column using ethyl acetate:acetone; 6:1 to give 6-isozorobyl'rGs (1,Q6
1; 65%). The product was fully acetylated (glysine/acetic anhydride) and the nmr spectrum was measured.

nmr (0DCJ5): r4.34 (djIH#
Jl, 23, OHz, H-1), 4.7 (2H
, H-2 and H-3).

5.36 (m s I H-H-4) -4,5 (d-
I H-Js', 4' 6-5 Hz -H-3'
), 4.55 (t# I H#: fj, s'
6.51 (z, H-4'), 7.84-7.9
(m, 12aa08H12), 8.8 4
C day, 3H, 0H3), 8.88
C.B.

3H,0H3).

Example 3 4,1',6'-)dichloro-4,6j1',6'
-tetradeoxygalactosucrose (6-deoxyT
GS) (a) 6-bromo 4,1',6'-)dichloro-4゜6.1',6'-tetradeoxygalactosucrose tetraacetate 2,3,3',4'-nato2-0- acetelium 4
゜1', 6'-) dichloro-4, 1', 6'-) lysoxy is pyridine (60 g) of lactosucrose (6 g)
d) Add the solution to triphenylphosphine (6,12,9)
,! : Treated with carbon tetrachloride (3,99), initially at 0°C for 1 hour and then at 65°C for 6 hours. TLO (ether:petroleum ether; 4:1) showed the presence of one, fast-moving product. Methanol (25 m
/) and then concentrated until it became syrupy. Elution of this syrup from a silica sol column with ether dipetroleum ether (2:1) produced the 6-bromo derivative, which crystallized from ether/petroleum ether.

(b) 4.1', 6'-trick four rows 4.1', 6.
A solution of the 6'-tetradeoxy product from the lactosucrose step (a) (1 g) in methanol was refluxed with 2N in the presence of barium carbonate (11). When reflux began, 10 minutes after adding hydrazine hydrate [1-] to the mixture, additional 1-hydrazine hydrate was added through the condenser tube. 30 minutes later,
The reaction mixture was filtered through a filter aid, then concentrated to a syrup and eluted from a small silica gel column with 1% aqueous ethyl acetate to give 6-deoxyT.
G8 was produced. [α] +87.1° (01,0, acetone); 130-NMR spectrum (D20 solution, relative value with DBS of circle standard as Oppm) Carbon atom Chemical Schiff), pJ) m2'
106.02 1 95.41 5' 83.75 3' 78.89 4I78-04 5 70.95 4 70.03 2 69.78. 15 69.28 1' 47.46 6' 45.99 6 19.61 4, 1', 6'-trichloro-4,6,1', <S
'-Tetradeoxygalactosucrose was found to be 400 times sweeter than sucrose (8T solution).

Example 4 6-0-benzyl TGS: 1,6-dichloro-1
゜6-zooxy-β-D-fructofuranosyl 4-chloro-4,-? Oxy-6-0-benzyl-α-D-galactopyranoside (a) 1, 2, 3, 3', 4', 6'-hexa-0-acetyl-6-o-benzyl sucrose (1
) 4.6-Benzylidene sucrose hexaacetate (
O reaction mixture in which Molecular Sheep Powder Type 3A (10,!9) was added to a THF (100rnI) solution of 101? 000 and to this was added sodium Schiff/ho hydride (NacNBu3) (15 g). After about 10 minutes, the reaction mixture was acidified with hydrochloric acid in diethyl ether until HCJ gas evolution ceased. The reaction was observed by TLC (ether). After about 1 hour, about 50 inches of product had formed. At this stage, more acidified ether was added and the reaction mixture was stirred for a further 1 hour.

TLO showed fil (90%) as the main product and some late or early products. The reaction mixture was diluted with dichloromethane (200y) and water and filtered through Celite. The organic layer was separated, dried over sodium sulfate, and concentrated to a syrup. The syrup was eluted from the silica sol column with ether dipetroleum ether (2:1) to yield (1) 9 g (90% yield)
I got it.

(B) 6-O-benzyl sucrose (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 Amberl
Neutralization with yst 15 (H+) ® and concentration yielded 2 (3 g, 95%).

(/J 6-o-benzyl-4,1',6'-trichloro-4,1',6'-)lysooxy-lactosucrose (3) A solution of 2 [2&, in DMF (10 ml)] was added to Bylsma The cells were treated with Ear's reagent (detailed method is described in British Tokkin No. 2079749) (prepared from DMF and PIJ), initially at 0°C for 20 minutes and then at 120°C for 8 hours. The reaction mixture was cooled to 20°C, methanol-ammonium hydroxide (2:1, ml) was added, and the temperature was increased to 5°C.
The temperature was maintained below 0°C.

The solution was concentrated and purified on a small silica sol column [using ethyl acetate:acetone (1:1)] to give 3(0
, 67g, 30chi), mp 55-57'c;' [α:
]9+5.8° was generated.

Mass spectral data [Ions marked (a) are hexapyranosyl (“galacto”) cations; (b)
) is the ketofuranosyl cation.

M/e 271a, 1991), 180a, 1631)
.

144a, 127b Example 5 Production of TGS from 6-benzyl ether (a) 6-o
-benzyl-4,1',6'-)dichloro-4',1
',6'-trideoxygalactosucrose tetraacetate (4) The product of Example 4 was combined with acetic anhydride (2-) and pyridine (5-).
When a conventional treatment was carried out using m7 at room temperature for 6 hours, 4 (0.68 g, 100 pieces) was produced.

(b) 4.1', 6'-)dichloro-4', 1'
, 6'-trideoxygalactosucrose (5)4
A sample of (500 μ) was dissolved in methanol (10,d) 8 and Raney nickel (1 tablespoon of medium sized spatl) was added. To this reaction mixture, add 1.5. d
of hydrazine hydrate was added. The mixture was then stirred at room temperature for 8 hours. TLC! [Ethyl acetate: Acetone:
water (/S:8:1)] showed one major product and one fast-moving side product.

The catalyst was filtered off and the reaction mixture was concentrated and loaded onto a silica sol column. Elution with ethyl acetate:acetone (1:1) as solvent produced TGS (51).

Example 6 6-0-benzyl TGE3 produced by benzylation of perchlorinated raw material (a) 4.1', 6'-) dichloro-4, 1',
A solution of 6'-)lysooxy-6-0-tritylgalactosucrose (6) Tos (20,!i') in pyridine (200 m/) was treated with trityl chloride (28 g) at 80°C for 1 hour. The reaction mixture was concentrated, taken up in dichloromethane, washed successively with water, aqueous bicarbonate, and water, and dried over sulfuric acid. The solution was concentrated and eluted from a silica sol column with diethyl ether to yield 6 (25 g, 77%).

Conventional acetylation of 6C109 with acetic anhydride (15ml) and pyridine (100td) for 6 hours at room temperature produced the peracetylated derivative 7 (12L, 95%).

(b) 2,3,3',4'-tetra-O-acetel-4,1',6'-trichloro-4,1',6
A solution of '-trideoxygalactosucrose (8) 7 (11 g) in a 60% acetic acid water bath (150 rnl) was heated at 90°C for 15 minutes.

TLO [:ether-volatile oil (4:1)] showed a slow moving product. Concentrate the solution to ether
Batheting from a coarse silica sol column with volatile oil (2:1) gave 8C6, 92 g, 90 t.

(c) Dichloromethane solution of 6-0-benzyl-4,1',6'-)dichloro-4,1',6'-trideoxygalactosucrose tetraacetate (4) 8 (5,0,!i') with excess benzyl trichloroimidate at 60°G.
It was treated for 6 hours. The reaction mixture was concentrated and diluted with ether-volatile oil (2:1). was eluted from a silica gel column using a silica gel column to yield 4 (1.7 g, 30%).

Treatment of 4 with a catalytic amount of sodium methoxide in dry methanol gives the same 6-0-
Benzyl TGS was produced.

Example 7 Production of TGS from 6-0-inzolovir-TGS 6-0
-Isozolopyl TGS (1.0g), 10-1N
Dissolved in hydrochloric acid and heated the solution at approximately 50°C on a water bath for several hours. The reaction mixture was then cooled, neutralized with sodium carbonate and evaporated in vacuo. The residue was then chromatographed on silica sol to yield pure TGS, identical to the standard sample.

In the example below, the methyl ether of TGS was converted to MTG
It is represented as S, and the 6-deoxy form is represented as DTGS.

Example 8 Beverage Sweetening Tablets Each tablet was packaged in an MTGB (8 ■) or DT case along with a dispersible tablet paste (approximately 60 ■) containing sucrose, gum arabic, and magnesium stearate.
Contains GS (10 ■) and is equivalent to the sweetness of approximately 4.5 g of sucrose.

Example 9 Bulk sweetener A bulk sweetener having the same taste as an equal volume of sucrose (granulated sugar) was mixed with the following ingredients to give 0.2 g/
Produced by spray drying to a bulk density of -.

Maltodextrin solution 22.2. F (dry weight)
The composition producing MTGS 2.0 g or DTGS 2.51 has a sweetening power equal to about 2 kg of sugar.

Example 10 Low calorie cola drink containing sugar 100ml. Ingredients for manufacturing bottled syrup MT
GS 80 da or DTGS 100 ■Sugar 6
0g Benzoic acid 65I (concentrated) Phosphoric acid 1-Cola 7L/
1.1-Coloring agent Add an appropriate amount of mineral water to make the total amount 100-.

Next, add this syrup to 225m7 of chilled carbonated mineral water! Each can be added in an amount of 25-.

Example 11 Ingredients for producing carbonated low calorie lemonade (sugar-free) 100- syrup: MTGS
100■ or DTGS 125q benzoic acid 35q citric acid (dry base) 1.67g lemon essence o, s,! 9 Make the total amount 100- with mineral water.

This syrup can be added in a dosage of 25 mg to each 225 - portion of chilled carbonated mineral water.

Example 12 Toothpaste Weight % Calcium hydrogen phosphate 50 Glycerin 20 Sodium lauryl sulfate 2.5 Spearmint oil 2.5 Gum tragacanth 1.0MTGS
O+03 water
23.97 ingredients are mixed to produce a spearmint flavored toothpaste with an acceptable sweetness but no sugar or saccharin.

Example 16 Chewing gum parts by weight Polyvinyl acetate 20 Butylphthalylbutyl glycolate 3 Polyisozotylene 3 Microcrystalline wax 3 Calcium carbonate 2 Flavor/Aroma 1 MTGS 0.07 or DTGS 0.09 Glucose 10 The chewing gum paste described above is made of ordinary tablets. Or can be cut into strips.

Attorney: Akira Asamura Procedural amendment (spontaneous) October 1986, Mr. Commissioner of the Japan Patent Office, 1. Indication of the case: Patent Application No. 169108, 1989. 2. Title of invention: sucrose derivatives 3. Person making the amendment. Relationship to the case Patent applicant 4, agent 5, date of amendment order 6, Showa year, month, day 6, number of inventions increased by amendment 7, specification subject to amendment

Claims (1)

[Scope of Claims] (1) A compound having the 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 isozoropoxy group. (4) Adding a sweetener to an ingestible product-spread oral composition, characterized in that the sweetener is a compound according to claim 1, provided that the sweetener is a hydrogen atom or a methoxy group. A method of mixing to sweeten the above ingestible products or oral compositions. (5) A sweet composition containing a sweetener mixed with an additive or a carrier, wherein the sweetener is a compound according to claim 1, where X is a hydrogen atom or a methoxy group. thing. +6) 4.1', <5'-)lichloro-4,1',
6',-)lysoxygalactosucrose, optionally protected at any of the 2, 3, 6', and 4' positions,
The general formula (
A method for producing a compound of the formula (wherein X represents an alkoxy or arylalkoxy group). (7) The method according to claim 6, wherein the starting material is protected as a 2,3-acetal. (8) (a) 4,6-0-benzylidene or 4.6-0-benzylidene esterified at the 1', 2.3, 6', 4' and 6' positions.
The 6-0-isozolobylidene sucrose derivative is reacted with a mild high-Pride type reducing agent to obtain 4-hydroxy-6-ether, and then (b) the product of step (a) is desorbed. Esterified to 6-0
- chlorination of the resulting 6-ether using a reagent that selectively chlorinates the 4,1' and 6' positions, or (c) After chlorinating the free 4-position and deesterifying it,
A process for producing a compound having the formula (wherein X represents a benzyloxy or isopropoxy group), characterized in that 1' and 6' positions are chlorinated. (9) The method according to claim 8, wherein the chlorinating agent in step (b) is Pilsmeier's reagent. 00) Claim 8, wherein the chlorinating agent in step (c) is triphenylphosphine and carbon tetrachloride.
The method described in section. (II) In the presence of hydrazine, 6-promo 4,
1'. A method for producing a compound having the formula (wherein X represents a hydrogen atom), which comprises reacting 6'-trichloro-4,6,1',6'-tetradeoxygalactosucrose with Raney nickel. (I2 4,1',6'-)lichloro-, characterized in that a compound having the general formula (wherein X represents an alkoxy or arylalkoxy group) is reacted with an ether cleaving agent
A method for producing 4,1',6-trideoxygalactosucrose. (13) The method according to claim 12, wherein x represents a benzyl group and the reagent is catalytic hydrogen.