JPS62209089A - Dolichylglucopyranosyl chlorophosphate derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [n is 3-22; X is H, acetamido or -OR<1>; R<1>-R<4> are -COQ<1> (Q<1> is lower alkyl or aryl) or -Q<1> (Q<1> is lower alkyl, aryl or aralkyl)]. EXAMPLE:2,3,4,6-Tetra-O-acetyl-D-glucopyranosyl chlorophosphophate. USE:A protein saccharification inhibitor and a carcinostatic agent. PREPARATION:Dolichyldichlorophosphate shown by formula II is reacted with a glucopyranose derivative shown by formula III in the presence of preferably 0.95-1.2 equivalent (based on the compound shown by formula III) basic substance (e.g. n-butyllithium, sodium hydride, etc.) preferably in a solvent such as THF, etc., at -70--60 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to the general formula (wherein n represents an integer of 5 to 22, X is a hydrogen atom,
Represents an acetamido group or 10R', R1, R2,
Rs and R4 are the same or different, each -COQ
' or -Q2, Qjij represents a lower alkyl group or an aryl group, and Q2 is a lower alkyl group.

A trisylglycopyranosylchlorophosphatate derivative (hereinafter referred to as chlorophosphae) represented by the following formula (hereinafter the same applies hereinafter) representing an aryl group or an aralkyl group.

(1)] and its manufacturing method.

The chlorophosphate (1) provided by the present invention is
Trisylglycopyranosyl phosphate [hereinafter referred to as phos-7ate (1)] represented by the general formula (wherein Y represents a hydrogen atom, a hydroxyl group, or an acetamido group; the same applies hereinafter) ] is useful as a synthetic raw material.

Trisylmannopyranosylphos7ate, trisylglucopyranosylphos7ate, trisylgalactopyranosylphosphate, trisyl 2-deoxyglucopyranosylphosphate, trisyl 2-acetamino-2-
Phos7ate (1), exemplified by deoxyglucopyranosyl phosphate and the like, is an important substance as a raw material for sugar components in the biosynthesis of glycoproteins necessary for the growth and life support of living organisms. For example, trisylmannopyranosylphos7ate, trisylglucobylanosylphosphate, and trisylgalactopyranosylphos7ate are trisyl diphosphate oligosaccharides, which are key intermediates in the biosynthesis of glycoproteins. It is known that it is incorporated into glycoproteins during the biosynthesis of glycosyltransferases (A, J-Parodi and L,
F.

Leloir, Biochim, B10ph:Y8
．． Acta 1979.559.1 and references therein). Also, Hos7ei) (1), Trisil
It is known that 2-deoxyglucopyranosylphos-7ate is incorporated into glycoproteins in the yeast body and inhibits the saccharification of the resulting glycoproteins.
hle and R,T.

Schwarz+ Eur, J. Biochem,
1976, 67, 239], and trisylmannopyranosyl phosphate is known to have an anticancer effect (see JP-A-59-155319).

Conventional technology Chlorophosphate (I) is a new substance that has not been described in the literature, and its chemical structure is an asymmetric dialkyl chlorophos 7
It can be considered a type of eight.

Conventionally, asymmetric dialkyl chlorophosphates include, for example, 2-chloromethyl-4-nitrophenyldichlorophosphate, N-7-1! Several asymmetric dialkylchlorophosphates derived from alkyl dichlorophos7ates such as thyl-5-iodo- or nitro-3-indolyldichlorophos7ate, methyldichlorophos7ate are known (L, A. 5l
otin, 5ynthesis 1977, 738). Glycodyl halides, 1,2-
Orthoester, 1,2-oxazoline, method using glycosyl-1-imidate, and method using glycosyl-1-0
- Methods using lithium or glycosyl-1-0-thallium salts have been reported (R-R-Schmi
dt and M-Stumpp, Liebigs A
nn-Chem, 1984.680 and references therein).

Problems to be Solved by the Invention As mentioned above, several methods for synthesizing asymmetric dialkyl chlorophosphates and alkyl 1-glycodyl phosphates are known. There are no examples of it being applied to the synthesis of

Furthermore, when the present inventors applied glycosyl halides, glycosyl-1,2-oxazoline, and cricosyl-1-imidate to the production of phosphoryl (1), it became clear that the reaction did not proceed.

Therefore, one object of the present invention is to be able to easily produce trisyl dichlorophos-7ate and a glycopyranose derivative in good yield and to easily induce phos-7ate (1) in good yield. The purpose of this invention is to provide a novel compound that Another object of the invention is to provide a method for producing the new compounds.

Means for Solving the Problems According to the present invention, the above object is achieved by providing the above-mentioned chlorophosphate (1), and trisyldichlorophosphate represented by the general formula [hereinafter referred to as this] dichlorophosphate 01)] and a glycopyranose derivative represented by the general formula [hereinafter referred to as pyranose (ff)] in the presence of a basic substance. This is achieved by providing a manufacturing method of I).

In the reaction according to the method of the present invention, the molar ratio of dichlorophos7ate (button and pyranose (IY)) is about 1:20 to
5:1. Preferably, the ratio is about 1:2 to 2:1. Examples of the basic substances used include organic lithium compounds such as n-butyllithium, butyllithium, tart-butyllithium, methyllithium, and phenyllithium; sodium hydride, potassium hydride,
Metal hydrides such as lithium hydride; lithium hexamethyldisilazide, sodium hexamethyldisilazide,
Examples include metal amides such as lithium tetramethylpiverazide, but n-butyllithium and sodium hydride are preferred from the viewpoint of ease of handling and availability. The amount of the basic compound used is in the range of about 0.8 to 2 equivalents, preferably about 0.95 to 1.2 equivalents, based on the amount of pyranose. This reaction is preferably carried out in the presence of a solvent. Examples of solvents that can be used include tetrahydrofuran and diethyl ether (hereinafter referred to as THF and diethyl ether, respectively).
ether], dimethoxyethane, 1,4-dioxate (7) x-thyl solvent benzene,
toluene.

Examples include aprotic solvents such as hydrocarbon solvents such as xylene, hexane, and pentane;
THF and ether are preferred from the viewpoint of ease of use.

The amount of solvent used is not critical, but it is about 1 to 100 times the weight of dichlorophosphate (I), preferably about 2 to 15 times the weight of dichlorophosphate (I). In addition, hexamethylphosphoric triamide (hereinafter referred to as 'tHMP') is used as an auxiliary solvent.
A], tetramethylethylenediamine, 1.5-
It is also possible to use an amine compound such as dimethyl-2-imidazolidinone or triethylenediamine in an amount of about 1 to 5 equivalents based on pyranose (I). The reaction is generally about −
Preferably, it is carried out at a temperature within the range of 100 to 0°C. The reaction time varies depending on the reaction temperature employed, but is usually about 2 to 24 hours. A preferred embodiment of this reaction includes n-butyllithium'! in a THF solution of pyranose (Iv) under an inert gas atmosphere. ! --70〜-
dropwise at 60°C, then dichlorophosphate (1)
of THFII solution was added under the same temperature conditions, and further HMPA
A method may be mentioned in which the mixture is stirred at -70 to -60°C for 12 hours after the addition of .

After the reaction is complete, chlorophosphate (1
) is carried out in the same manner as in the method used for separating and purifying products obtained by general organic synthesis reactions from reaction mixtures. For example, the reaction mixture is poured into water, extracted with an organic solvent such as ether or chloroform, the organic layer is dried, the solvent is distilled off, and the residue is fractionated by column chromatography to obtain chlorophos 7. Eight (1) can be obtained.

By subjecting the thus obtained chlorophosphate (+) to a hydrolysis reaction and then subjecting the product to a deprotection reaction, cyphos 7ei) (II) can be easily produced. . Note that the reaction mixture containing chlorophosphate (1) produced by the above reaction can also be directly subjected to the hydrolysis reaction.

The hydrolysis reaction is easily carried out in an ethereal solvent such as THF or ether in the presence of an organic amine or an alkali metal or alkaline earth metal hydroxide. Although the amount of solvent used is not critical, chlorophosphate (1)
The amount is about 1 to 100 times the weight, preferably about 2 to 15 times the weight.

As the organic amine, for example, tertiary amines such as pyridine and triethylamine are used. alkali.

Examples of metal hydroxides used include sodium hydroxide and potassium hydroxide, and examples of alkaline earth metal hydroxides include barium hydroxide and calcium hydroxide. The amount of organic amine or alkali metal or alkaline earth metal hydroxide used is chlorophos7.
About 1 to 5 equivalents, preferably 1.1 to eight (1)
~2 equivalents. The reaction is generally about -20 to 20
The reaction is preferably carried out at a temperature within the range of .degree. C., and is usually completed in about 1 to 15 hours, although it varies depending on the reaction temperature employed. The deprotection reaction is classified into a solvolysis reaction and a dissolved metal reduction reaction depending on the protecting group of chlorophos(7) (1). When the protecting group is a lower alkanoyl group such as an acetyl group or an aroyl group such as a benzoyl group, a solvolysis reaction such as a hydrolysis reaction or an alcoholysis reaction is employed as the deprotection reaction. The hydrolysis reaction is usually carried out in the presence of an alkali, and the alkali is lithium hydroxide.

Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are used. This reaction can also be carried out in the presence of a co-solvent such as THF or chloroform. The reaction is generally preferably carried out at a temperature in the range of about 0 to 20°C, and is usually completed in about 1 to 12 hours, although it varies depending on the reaction temperature employed. The alcoholysis reaction is usually carried out in the presence of a metal alkoxide. Examples of alcohols used in this reaction include methanol and ethanol, and examples of metal alkoxides include sodium methoxide and sodium ethoxide. The metal alkoxide used in the reaction is usually about 0.5 to 5
% of the corresponding alcohol solution, and used in such an amount that the pH of the reaction mixture becomes strongly alkaline (>12).This reaction can also be carried out in the presence of a co-solvent such as chloroform. The reaction is generally preferably carried out at a temperature in the range of about -20 to 20°C;
Although it varies depending on the reaction temperature used, it usually takes about 30 minutes or more.
It will be completed in about 10 hours. In addition, chlorophosphate (
When the protecting group in 1) is a heptaralkyl group such as a benzyl group, a dissolved metal reduction reaction is employed as the deprotection reaction. The dissolved metal reduction reaction is carried out by the action of an alkali metal such as lithium or sodium in an amine such as ammonia, methylamine, or ethylamine.

It is also possible to use organic solvents such as THF and ether as auxiliary solvents. This reaction is generally about -50
The reaction is preferably carried out at a temperature in the range of -0°C, and is usually completed in about 1 to 10 hours, although it varies depending on the reaction temperature employed. After the completion of each of the above reactions, separation and purification of the phosphate from the reaction mixture is carried out in the same manner as used for separation and purification of products obtained by general organic synthesis reactions from the reaction mixture. .

Dichlorophosphate (1), which is used as a raw material in the method of the present invention, can be easily prepared by reacting phosphorus oxychloride with dolicol represented by the corresponding general formula [hereinafter referred to as dolichol (f)]. Obtainable. The general formula % formula %) represents the unit of the above-mentioned Dolichol ff), and k represents an integer from 12 to 18. In this specification, dolichol (hereinafter referred to as dolichol (mer 1)) represented by It is easily available as a mixture of

Number of cis-type inprene units (k) Composition ratio (4)
12 0.1 ~ 61
5 4-1714
20-3515
30-5016
10-2517
2-1018
0.1 to 5 If necessary, it is also possible to isolate the above mixture according to molecular weight and use a single homolog as a raw material for the present invention, or two or more of these homologues can be used as a raw material for the present invention. It can also be used as a mixture in any proportion. It can also be produced by using polyprenol or a mixture thereof having an appropriate number of inprene units and extending saturated isoprene units according to the method disclosed in the above publication.

Pyranose used as a raw material in misfires is
It is easily prepared by known methods. For example, 2.5,
Both anomers of 4.6-tetra-0-acetylmannopyranose were prepared from commercially available mannose by Bonner and W
It can be prepared according to the method of Arren et al.
W, A, Bonner+ J, Am, Chem,
Sac,, 1958.80°3572 and CD
, Warren et al., + J. Biol.
Chem.

1975, Kei 4, 8069 Reference n. Also, 2,3
Both anomers of , 4.6-Citler O-7 cetylglucopyranose were obtained from commercially available glucose.
can be prepared according to the method of n (M-L, W
olfrom and A.

Thompson, Methods Carbohy
dr, Chem, 1963.2゜212; G
, N. Bollenback at al-+ J-A
m, Chem, 5oc-t1955, 77, 3310
i and P, Z, A11en, MethodsCa
rbohydr-Chem,, 1965.2.372
reference). Also, 2.3.4.6-chitra-O-benzylmannopyranose and 2,5.4.6-tetra-0-
Benzylglucobylanose can be prepared from commercially available methylmannopyranoside or methylglucopyranoside by the method of Koto et al. (S-K
ot.

et al, Bull, Chem, Soc,
Japan, 1 q76+dan, 2639).

EXAMPLES The present invention will be explained in detail with reference to examples below, but the present invention is not limited to these examples. In the examples, measurements were made using 'H-NMRViCD C1s as a solvent and tetramethylsilane as an internal standard, and IR was measured using a liquid film. Note that dolichol (Y-1) used as a raw material in the examples is a mixture of homologs having the composition ratios shown below.

Number of cis-type isoprene units (k) Composition ratio ((a) 12 1.5
1!5 7.414
27, 115
37.616
17.817
6.418
2.2 Example 1 Oxychloride lJ/2 was placed in a three-necked flask purged with argon.
40 μIt was added thereto, and the mixture was stirred while cooling in ice-methanol. Dolichol (V-1) is added to this phosphorus oxychloride.
．． A THF solution of 999 (0.76 mmol) and 180 μl of triethylamine was slowly added dropwise. After the addition was completed, the reaction mixture was stirred for 1 hour, and the solvent, excess phosphorus oxychloride, and triethylamine were distilled off under reduced pressure. The residue was suspended in ether, the insoluble matter was filtered off, and concentrated under reduced pressure.Then, the concentrate was diluted with 10 g of THF,
It was made into a dichlorophosphate solution. 50 of 2,5,4.6-Chitler O-acetel-β-D-glucobylanose
0 Misaki (0.85 mmol) was dissolved in THF3at and stirred at -70°C under a 7/l/-f:y atmosphere. To this solution, 0.47 d of 1.82N n-butyllithium hexane solution was added, followed by the previously prepared dichlorophosphate solution, and then 0.47 d of HMPA
．． 15gt was added and stirred at -70 to -60°C overnight.

The reaction mixture was poured into water, the organic layer was separated, and the aqueous layer was extracted with ether. The organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (Merck, Art,
7734, Kieael-gel 6070-2
30 mesh.

Trisyl 2,3,4.6-Citler O-7 Cetyl-D-glucopyrano 6,041,111 silchlorophos-7ate were obtained. The yield is dolichol (,
V-1) was 47%.

IR(3-') ν(film): 1755,1
665,1230°985,840.750'H-NMRδ: 0.92 (3H), 1.0~
zs (144H).

22m 57-5.8 (27H) Reference Example 1 Trisyl 2.5,4.6-tetra-0-acetyl-D-glucopyranosylchlorophosphate'kT obtained in Example 1 Dissolved in 15 ml of HF Then, 7.3 mef of a 0.2N aqueous sodium hydroxide solution was added to this mixed solution while stirring under water cooling, and the mixture was stirred at room temperature for 4 hours.

Separate the organic layer of the reaction mixture, extract the aqueous layer with ether,
The organic layers were combined and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and trisyl 2.5,4.6-tetra-0
-acetyl-D-glucopyranosyl phosphate was obtained. This product was dissolved in chloroform, and a solution of sodium methoxide in 1-thimethanol was added until the pH of the reaction mixture became 12, followed by stirring at room temperature for 1 hour. Next, an ion exchange resin (manufactured by Bioland) was added to the reaction mixture.

AG 50W-X8200-400mesh and pyridinium type were added to neutralize the mixture, and after filtration, the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (Merck, Art, 7754. Kieselgel)
60.70-2370-23O, eluent: Volume ratio of chloroform and methanocyto-28thiammonia water 75:
25:1 mixture) to obtain 558 trisyl D-glucopyranosylphos 7ate. The yield was 65% based on chlorophos 7ate.

IR(3)j' (film): 3350.1665
, 1230°985, 840.750' H-NMRδ: 0.92 (3HL 1.0~
2.3 (152H).

22m 52--8 (27H) Example 2 By carrying out the reaction and separation operation in the same manner as in Example 1 except for using ether instead of THF,
Trisyl 2 having substantially the same instrumental analysis value as Trisyl 2゜5.4.6-Citler O-acetyl-D-glucopyranosyl chlorophosphate obtained in Example 1
, 590 capes of 5,4.6-tetra-0-acetyl-D-glucopyranosylchlorophosphate were obtained. The yield was 46% based on Dolichol (V-1).

Example 5 Trisyl 2,3,4,6-tetra-0-acetel-D-gluco obtained in Example 1 was obtained by performing the same reaction and separation operations as in Example 1 except that HMPA was not used. Trisyl 2,3,4.6- with substantially the same instrumental analysis as pyranosyl chlorophosphate
Tetra-0-acetyl-D-glucopyranosylchlorophosphate 't521wll was obtained. The yield is dolichol (
It was 41 arrogant based on Mar 1).

Example 4 Trisyl 2,3, Trisyl 2,3,4.6- with substantially the same instrumental analysis as 4.6-tetra-O-acetyl-D-glucopyranosylchlorophos7ate
445η of tetra-0-acetyl-D-curcopyranosylchlorophosphate was obtained. The yield is dolichol (Y-
Based on 1), it was 34 chi.

Example 5 In Example 1, 2.
Trisyl 2,3,
4.6-Tetra-0-acetyl-D-mannopyranosylchlorophosphate f, 612W was obtained. The yield was 48% based on Dolichol (Y-1).

Engineering R (cll) ν (Film): 1755,1
665,1230°985,840.750' H-NMRδ: 0.92 (3H), 1.0
~2.3 (144H).

22m 3.7-5.8 (27H) Example 6 In Example 1, 2,3,4.6-Chitler O-acetyl-β-D-glucobylanose 300W was replaced with 2
．． 3.4.6-Tetra-0-benzoyl-β-D-glucobylanose was used in the same manner as above except that 500 d of trisyl 2,3,4
．． 645"lJ of 6-tetra-0-benzoyl-D-glucopyranosylchlorophosphate was obtained. The yield was 45"lJ based on dolichol (v-1).

IR (ffi) ν (film): 1730,1
665,1600°1500,1230.985.84
0.750'H-NMRδppm: 0.92 (3H
, l, 1.0-2.3 (132H).

5. 7~5.8<27H), 7.5~a2(zoH)
Example 7 In Example 1, 2.
Trisyl 2.5.4.6-tetra-O-benzyl-D-glucopyrano 61,311 g of silchlorophosphate was obtained. The yield is dolichol (V-1
) was 43%.

IR(ffi) ν(film): 1665,1
600.1500°1230, 985.840.750' H-NMRδ: 0.92 (3H), 1.0
~2.3 (132H).

22m 57-5.8 (35H), 7.2 (20H) Example 8 In Example 1, 2-2- in place of 300 da of 2.5,4.6-Chittler O-acetyl-β-D-gelcopi2nose
Trisyl 2-deoxy-3,4,6-)di-0 5851v of -acetyl-D-glucopyranosylchlorophosphate was obtained. The yield was 47's based on dolichol (Y-1).

IR(cll)y<finim): 1755,16
65,1230°985.840,750' H-NMRδppm: 0.92 (3H),
1.0-2. ! l (142H).

3.7-a8 (27H) Example 9 In Example 1, 2,3,4,6-Citler O-acetyl-β-D-glucobylanose 300 W was replaced with 2
-Deoxy-2-7cetamino-3.4.6-tri〇-acetyl-D-glucobylanose 500 Misaki was used, but the reaction and separation operations were carried out in the same manner.
Trisyl 2-deoxy-2-acetamino-3,4,
645 Da of 6-tri0-acetyl-D-glucopyranosyl chlorophosphate was obtained. The yield was 48 units based on dolichol (1 unit).

IR(ll'll-') v (film): 1
755,1655,1530°1230,985.84
0.750'H-NMRδppm: 0.92 (5H), 1
．． 0-2.3 (144H).

57-6. +(28H) Example 10 Dolichol (V-1) 0.9 in Example 1? Trisyl 2,5,4°6-
Chitler O-acetyl-D-glucopyranosylchlorophosphate 7-eight [corresponds to a trisylglycopyranosylchlorophosphate derivative in which n is 8 in general formula (1)]
I got 242 da. The yield was 25% based on dolichol.

IR(cll-') W (film): 175
5,1665,1230°985,840.750'H-NMRδ: 0.92 (3H)
, 1.0 to 2.3 (81H hapm F ~ 5.8 (27HJ Example 11 In Example 1, dolichol (V-1) 0.999 was replaced with general formula ff) where n is 3. By performing the reaction and separation operation in the same manner except for using 0.30 g, trisyl 2,5,4゜6-chitler O-acetyl-D-glucopyranosyl chlorophosate [n in general formula (1) 21,211g of trisylglycopyranosylchlorophosphate derivative with 3 is obtained.The yield is 26% based on dolichol.
It was Chi.

IR(aI-') y (fil A): 1755
, 1665, 1230°985, 840.750' H-NMRδ, -: 0.92 (3H), 1.
0-2.3 (56H).

3.7 to 5.8 (27H) Example 12 Same as in Example 1 except that Dolichol 300 #, in which k is 15 in the general formula (Y-1), is used instead of Dolichol (V-L) 500 #. By performing the reaction and separation operations under the following conditions, the instrumental analysis value was substantially the same as that of trisyl 2,5,4,6-chitler O-acetyl-D-glucopyranosyl chlorophosphate obtained in Example 1. trisyl 2゜3.4.6-tetra-0-
Acetyl-D-glucopyranosylchlorophosphate [
Corresponding to the trisylglycopyranosylchlorophos7ate derivative in which n is 17 in general formula (1)] is 595q
Obtained. The yield was 46% based on dolichol.

Example 15 Phosphorous oxychloride 24 was added to a three-necked flask purged with argon.
0 μl was added and stirred while cooling in ice-methanol. Dolichol (mer 1) is added to this phosphorus oxychloride.
A THF solution of 991F (0.76 mmol) and 180 μl of triethylamine was slowly added dropwise. After the addition was completed, the reaction mixture was stirred for 1 hour, and the solvent, excess phosphorus oxychloride, and triethylamine were distilled off under reduced pressure. The residue was suspended in ether, and after filtering off insoluble matter, it was concentrated under reduced pressure.Then, the concentrate was diluted with 10 g of THF to obtain a dichlorophosphate solution. 2,3,4.6-
Tetra-0-acetyl-β-D-glucobylanose 5
00 Misaki (o, 85 mmol) was dissolved in THF5Nt and stirred at -70°C under an argon atmosphere. Add 0.0% of 1.82N n-butyllithium hexane solution to this solution.
47 ml was added, followed by the previously prepared dichlorophosphate solution, and further 0.15 s+t of HMPA was added, followed by stirring at -70 to -60°C overnight. 7.5 ml of 0.2N aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was stirred at room temperature for 4 hours. The organic layer was separated, the aqueous layer was extracted with Nitera, the organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (Merck, Art, 77).
54, Kieselgel 60.70-270-
Eluate: Volume ratio of chloroform, methanol, and 28% ammonia water: 20:
Trisil 2.3.
4.6-tetra-0-fucetyl-D-glucopyranosyl phosphate 581! Obtained. The yield is dolichol (V
- It was 45% based on IJ.

IR (alt") j' (film): 1755
．． 1665.1230?85.840.750'H-NMRδppm: 0.92 (3H), 1.
0-2.5 (144H).

5.7-5.8 (27H) Effects of the Invention According to the present invention, as is clear from the above examples, chlorophos-7ate (Iv) can be easily produced in good yield from dichlorophosphate (1) and pyranose (Iv). ) can be produced, and as is clear from the reference examples, cyclophosphite (1) can be easily derived into phosphate (1) in good yield.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, n represents an integer from 3 to 22, X is a hydrogen atom,
Represents an acetamido group or -OR^1, R^1, R
^2, R^3 and R^4 are the same or different and each represents -COQ^1 or -Q^2, Q^1 represents a lower alkyl group or an aryl group, and Q^2 represents a lower alkyl group, an aryl group. or an aralkyl group). 2. In the general formula, R^1, R^2, R^3 and R^
The dolysylglycopyranosylchlorophosphate derivative according to claim 1, wherein 4 is an acetyl group or a benzoyl group. 3. In the general formula, R^1, R^2, R^3 and R^
The dolysylglycopyranosylchlorophosphate derivative according to claim 1, wherein 4 is a benzyl group. 4. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n represents an integer from 3 to 22) Dolysyl dichlorophosphate and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. In the formula, X is a hydrogen atom, an acetamido group, or -OR^
1, and R^1, R^2, R^3 and R^4 are the same or different, and are -COQ^1 or -Q^2, respectively.
(wherein Q^1 represents a lower alkyl group or an aryl group, and Q^2 represents a lower alkyl group, an aryl group, or an aralkyl group) in the presence of a basic substance. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, n, X, R^2, R^3 and R^4 are as defined above). A method for producing a nosylchlorophosphate derivative. 5. In the general formula, R^1, R^2, R^3 and R^
5. The method for producing a dolysylglycopyranosylchlorophosphate derivative according to claim 4, wherein 4 is an acetyl group or a benzoyl group. 6. In the general formula, R^1, R^2, R^3 and R^
5. The method for producing a dolysylglycopyranosylchlorophosphate derivative according to claim 4, wherein 4 is a benzyl group.