JPS6363659A - N-phthalimide derivative, production thereof and production of polyamine using said derivative - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (n is 0-7 integer; Phth is phthaloyl; Ts is tosyl; X is O or NH). USE:An alkylating agent especially useful for polyamine syntheses. PREPARATION:A compound shown by formula II (n is 0-3 integer; Y is Br or 0Ts) is reacted with a compound shown by the formula PhthN<->M<+> (M is alkali metal atom) to give a compound shown by formula I. A compound shown by formula III in the compound is obtained by subjecting a compound shown by formula IV to N-nitrosation and treating the prepared compound shown by formula V in benzene. A compound shown by formula IV (n is 1-7 integer) in the compound shown by formula I is obtained by reacting the compound shown by formula III with a compound shown by formula IV (m is 0-3 integer). Further a polyamine shown by formula VII (l is m+2n+2) can be produced by reacting the compound shown by formula III (n is 0-7 integer) with a compound shown by formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel N-phthalimide derivative, a method for producing the same, and a method for producing polyamine using the same.

[Conventional technology]

In order to continuously extend the polyamine chain, a reactive alkylating agent having an overprotected amino group at one end is used.
It has been sought after in the field of synthetic polyamine chemistry. As such an alkylating agent, N-(ω-bromoalkyl)phthalimide is said to be the best [Salberg et al., Organic Synthesis (P, L, S
Alzberg et al.

Org, 5ynth), Co11. Vol, L 11
9 (1941); Sheehan et al., Journal of the American Chemical Society (J, C, 5he
ehan etal, J, Am.

Chem, Soc, ) 72.2786 (1950
)), but this compound is characterized by the reactivity of the bromo group, limited preparation methods for general use, and instability under the basic conditions normally required for alkylation reactions. For this reason, there was a problem that it could not be universally used as an alkylating agent.

[Problem that the invention seeks to solve]

It is therefore an object of the present invention to provide new N-phthalimide derivatives which can be particularly useful alkylating agents for polyamine synthesis.

Another object of the present invention is to provide a method for producing 35 N-phthalimide derivatives.

Still another object of the present invention is to provide a method for producing a polyamine using the N-phthalimide derivative.

[Means for solving problems]

The above object of the present invention is achieved by an N-phthalimide derivative represented by the following general formula.

(In the formula, n is an integer of O to 7, phth is a phthaloyl group,
T represents a tosyl group, and X represents 0 or NH. ) Specific examples of the N-phthalimide derivative of the present invention represented by the above general formula are shown below.

(2a) n=0 (2b) n=1(2c
) n=2 (2d) n=3(6a) n
=o (6b) n=1(6c) n=2
(6d) n=3 (6e) n=4
(6f) n=5 compounds (2a) to (2d), (6
a) to (6d) are, for example, represented by the general formula (I) (wherein, n is an integer of 0 to 3, Ts is a tosyl group, X is 0 or NH, and Y is a bromine atom or OTs). The compound (1) is reacted with a compound represented by phthN-M" (Phth is a phthaloyl group, M is an alkali metal atom).

Examples of compounds represented by the general formula (7a)
n=o (9a) n=0(
7b) n=1 (9b)
n=1 (7c) n=2 (9c
) n=2(7d) n=3
(9d) n”3 is mentioned.

Compounds (2a) to (2d) are also compounds (6a) to
(6d) using the method of Iwata et al. (Bull).

Che++, Soc, Jpn,, 58.339
5-339'6 (1985)) to obtain a compound represented by the general formula 〇〇, and the compound is synthesized by treating the compound in Hensen.

Compound (61 (n=1-7) is compound (2a) ~(
2d) and a compound represented by the general formula (b) (in the formula, m represents an integer of O to 3).

By reacting the compounds (2a) to (2d) with the compound represented by the general formula
is m+2n+2. ) can be produced.

A specific example of "PhthN-M" is "PhthN-K"
, PhthN-Na'', PhthN-Li'', and the like.

A specific example of the above reaction is shown in the following scheme.

Steps A-D are dimethylformamide (DMF)
1.1 to 1.2 molar equivalents of the compound (
4) is preferably carried out in the presence of.

Compounds (2a), (2b), (
2c), (2d), (3), (6a), (6b), (6
C), (6d), (6e), (6f), (9C), (9
d) (10a), (10b), (10c), (10d), (
11a), (1l b>, (11C), (11d), (
13a), (13b), (13c), and (13d) are all new compounds.

〔Effect of the invention〕

The compounds of the invention are reactive synthons in the N-alkylation of α,ω-disulfonamides and can be used in various fields of organic synthesis.

In addition, the phthalimide group can be easily removed by conventional methods, and the resulting amine can be easily tosylated, so the compounds of the present invention can be used to easily synthesize open-chain polyamines with arbitrary chain lengths. .

Hereinafter, the present invention will be explained in more detail with reference to Reference Examples and Examples.

Reference Example 1 (Synthesis of Compound (3)) (i) Commercially available 2-bromoethylamine hydrochloride was tosylated with pyridine-tosyl chloride to obtain N-(2-bromoethyl)-tosylamide (5).

This reaction has been described by Iwata et al., Bull, Chem, Soc.
Jpn,.

59, 1031-1036 (1986).

(ii) Compound (5) is then nitrosated, /-1-
-\Br N Ts (N (2-bromoethyl)N.

-N-nitrosotosylamide), but the general method of nitrosation is improved from the conventional method and is described in the literature;
wata and H, Kuzuhara, Bull
, Chem.

Soc, Jpn, 58.3395-3396 (19
The following procedure was carried out using the method reported in 85).

Compound [5] (2.78g, 10IIImO1) was dissolved in a mixed solution of acetic anhydride (20mf> and acetic acid (6ml), and sodium nitrite (1.7g, 2emmoβ) was added to it while keeping the temperature at about 10°C. , are added little by little to prevent the reaction from becoming too intense. After the addition, stir the reaction at the same temperature for 30 minutes, then add water (50 ml) while cooling.
) to stop the reaction. In order to decompose excess acetic anhydride, the mixture was stirred at this temperature for an additional 30 minutes, and then benzene (50 ml) was added to extract the nitroso compound. After drying the benzene layer over anhydrous magnesium sulfate, the benzene layer was concentrated under reduced pressure at a low temperature of 50° C. or lower, yielding 2.71 g (yield 88%) of Br N T3.

Obtained as a yellow liquid; Elemental analysis; (calculated value) S, 10.44″t,
Br, 26.02χ (observed value) S, 10.96χ,
Br, 26.082IR (KRS); 1375.
1186.1170 (SOz) cm-'.

1510 (NO) cm-'.

/-111\ (iii) Next, the Br NTs are rearranged to form N.

l--1-\ leads to Br OT, but the general method of this rearrangement reaction is described in the literature (M, Iwata and H
, Kuzuhara+ g, Chem, Soc,
CheLIl, Commun.

■Based on the method reported on page 918-919),
It was carried out as follows.

N.

m 12 ), stirred and reacted at about 80° C. for 17 hours (after confirming that the nitroso form had disappeared on TLC), and then benzene was removed under reduced pressure. The residue was developed with benzene through a silica gel column to purify the product portion, yielding 0.4 g (80%).

Elemental analysis; (calculated value) C, 38, 72, H, 3, 9
7°S, 11.49. Br, 28.63: (observed value) C, 39,02, H, 4,02°S, 11.6
1. Br, 28.332IR (KRS); 13
60,1189.1170(SOz)c+n-'.

'II-NMR (CDCβ3): δ 2-46 (3tl + s + A r
-C! I 3 ) 3.47 (2H, t+ J=6
．． 56. Br-(lj2)4.29 (211,t
, J=6.56. 0-C! ! 2) 7.36 (2
H, d, J・8.10. aromatic nucleus proton) 7.81
(2H, d, J=8.10+ aromatic nucleus proton) Compound (3) and N-(2-bromoethyl)-N-nitrotsylamide are new compounds.

Reference Example 2 (Synthesis of compound (9)) Iwata et al.'s method (Bull, Chem, Soc, JP
Compound (2) synthesized by the method of Iwata et al.
Chem, Soc, Jpn,, 58°3395
(1985)). The properties of the obtained dinitroso body O vessel are shown below.

[Properties of compound Q4)] n=o yield 96.5χ, Rf=0.70 (solvent,
Chloroform:acetone 95:5 v/v) n=1
Yield 95χ, mp 108-110℃ elemental analysis;
(Calculated value') C, 48, 14, H, 4, 69°N,
11.23. S, 15.42Z (observed value) C,
48,03,11,4,70°N, 10.93.
S, 15.27χIR (KBr); 1510 (
NO) cm-'1375.1350,1169,115
5. (Sot) cm-'n=2 Yield 98χ,
mp 203-204℃ elemental analysis; (calculated value) C, 4
9,74,) 1.4.91°N, 10.24. S
, 15.62χ (observed value) C,49,50,Il,
4.91°N, 10.12. S, 15.48
χIR(KBr): 1509 (NO)cn+-'
1380, 1345.1170.1155. (SOz
) cm-'n=3 Yield 92χ, I'1f=0.
55 (solvent benzene:ethyl acetate 9:1 v/v)
This dinitroso isomer was prepared using the method of Iwata et al. (J, Chef
i.

Soc, Chem, Commun,, 918 (
A rearrangement reaction was carried out according to (1985)) to obtain compound (9).

[Properties of compound (9)] n=o mp 118-120°C Elemental analysis; (calculated value) C, 51, 87,) I, 4
．． 90°S, 17.31% (observation direct) C, 51, 68,' I, 4.
85°S, 17.06χ IR (KBr); 1360.1190.1178 (
SO □) cm-'lowit-NMR (CDCl 3)
:δ 2.46 (3) IX2. s, Ar-Cdan,
)4.18 (2Hx2.s, 0(C)Iz)zo
) n=1 (Known substances D, H, Peacock a
nd L! , C. Dutta.

J. Chem. Soc., 1934.1303
)n=2 mp 149450℃ Elemental analysis; (calculated value) C, 53,38, H, 5,2
7°N, 3.66, S, 16.77χ (observed value) C, 53, 13,! ! , 5.18°N, 3.67
, S, 16.85χ IR (KBr): 1350, 1!89, 1175,
1150 C3Oz)cn+-''H-NMR (CDC
13): 62.44 (3H x 4. s, Ar-C Dan 3) 3.30 (2H x 2. s, N (CHz)
zN) 3.36 (2HX2.t, J=5.
37. NCdan2C11゜0)4.14 (2)1
x2. t, J=5.37. NC11zCH
zO)n・3 Amorphous powder elemental analysis; (calculated value) C, 53,67, H, 5,3
4°N, 4.37. S, 16.66χ (observed value) C, 53,35, H, 5,39°N, 4.
39. S, 16.47X IR (KBr): 1345, 1187, 1172.
1155 (SOz)cm-''H-NMR (CDC1
3): δ 2.42.2.43.2.46 (3Hx2. 3Hx2.3H,s, Ar-C 几,)
3.29 (2HX4.m, N(Cshi)2N)3.
40 (2Hx2.t, J=5.62.NCdan2CI(20)4.15 (2Hx2.t, J=5
．． 62. NCH2C Dan 20) Reference Example 3 (Compound (7)
Synthesis) Compound (7) was synthesized in the same manner as in Reference Example 2. That is, during the rearrangement reaction of the dinitroso isomer (9) and 17)
Since they occur simultaneously at a certain rate, they were separated.

[Properties of compound (7)] (7a) (n=0) Amorphous powder elemental analysis; (calculated value) C, 52, OL jl,
5.18°N, 3.79. S, 17.36χ(
Observed value) C, 51, 82, H, 5, 14°N, 3.6
6, S, 17.16! IR (KBr): 3300 (NH) cm-'13
50, 1330.1188.11', 5°1155 (
SO2)cm-'')l-NMR (CDCR3): δ 2.43.2.46, (3H+ 3H,s, Ar
-CH5)3.22 (2H,q, J=5.37,6
．． 34. ) for iN-C 2) 4.05' (2) 1.
t, J・5.37. QCC205,01(IH,t
, J=6.34. TsN and) (7b) (n=1)
mp 144-146℃ elemental analysis; (calculated value)
C, 52,98, H, 5,34°N, 4.94. S
, 16.98χ (observed value) C, 53, 12, 11, 5, 33°N, 4
．． 98. S, 16.85χIR (KBr);
3300 (Nil) cm-'1362, 1
325. 1190. 1175°1155 (SOz
)cm-''H-gate R (CDC7!3): δ 2.43. 2.46 (311x2.38
．． s, r-CH3)3, 14.3.16 (
211X 2. m, N(C)Iz) zN)3.
34 (2)1. t, J=5.62. NCH2
CH2o)4.10 (2H,t, J=5.62.
NGHzCHzO) (7c) (n=2); mp
129-131”c elemental analysis; (calculated value) C, 53
,45,)I, 5.4LN, 5.50. S, 1
6.79χ (observed value) C, 53, 32, +1.5.51
°N, 5.21. S, 16.78χIRf:KB
r); 3300 (NH)cm-'1340
．． 1190,1176.1160 (SOz)cm-
'') l-NMR (CDCl 3): δ 2.40. 2.44. 2.45 (3H, 3H,
3HX 3. s, Ar-C and 3) 3.16 (2H
,Ia, TsNHCHHz)3.18 (28,n+
, TsNCHz(:1lzN)3.36 (21
1, t, J=5.12. TSNC)IZCI!
, 0) 4.13 (2H, t, J=5.12.
TssCHzCLO)5.12 (l)l, t
, J□5.6B, TsNHClz) (7d
) (n・3): Amorphous powder elemental analysis; (calculated value) C, 53, 73, H, 5, 4
5°N, 5.83. S, 16.68χ (observed value)
C, 54,08, +1.5.50°N, 5.76,
S, 16.38χIR (KBr); 330
0 (N)I)cm-'1340.1190.117
5.1155 (802)C-1')l-NMR: δ 2.40. 2.43. 2.44. 2.46
(3H,3HX2,3H53H,s,Ar-C11,,
)3.18 (2HX2. m, N(C and z)
zN) 3.30-3.36 (2Hx4.m, N(C
and Z) 2N) 3.41 (2H, t, J・5.
61. NC…ZCH20)4.15 (2H,t
, J・5.6L NC)12cdan20)5.35
(IH, t, TsNfiCHz) Examples 1 to 6 U 9c 4 2c 10c9c (
0.55g) in dimethylformamide<DMF) (
30 mN), to which 1.2 equivalents of 4 (0,1
After stirring and reacting at 5 to 15°C for 40 hours, the resulting precipitate was collected and subjected to silica gel chromatography, and chloroform:acetone (97:3 v/ v), 0.18g (34%) of 15 and 0.1g of 10c
8g (35%) was obtained.

Properties of (1): mp 153-154°C elemental analysis; (calculated value) C, 56,81, if 5.04°N
, 5.68. S, 13.00χ (observed value) C156,7? , H2S-03+N, 5.
60. s, 13.04: IR (KRS): 1775,1710(CO)cm
-'1350.1189.1172.1155 (S
O2) cm-''H-N AR (CDCl 3): δ 2.44.2.45.2.46 (3H138+ 3H,s, Ar-C River,)3.43
,3.46(2HX3.m, phthNCH2C几z
jjcllzc)iz)3.62 (2H,t,
J"5.86. -NCHzCHzOTs)s 3.80 (2) 1.t, J=5.38.ph
thN-C)lz)4.26 (2H,t, ,I'
5.86. (:)lzcil□0Ts) (10C)
Properties: mp 221-222°C elemental analysis; (calculated value) C, 60,49, H, 4,80°N, 7.84.
S, 8.97χ (observed value) C, 60, 41, H, 4, 79°N, ?
, 76, S, 8.89χ IR (KRS): 1775, 1712 (Co)
cm -'1376.1332,1148(Sot)c
m-''H-NFIR(CI)Cl3):62.3
7 (3HX 2.s, Ar-Cl1s)3
, 43 (28X 2.t, ph thNC
HzCdanKN) 3.61 (2HX 2.t,
phthNclI□CLFi(Jjz)3.95
(2HX 2.t, phthNCdan 2C) +2
) Similarly, compounds Th(2a), (2b), (2d),
(10b), # and (10d) were obtained.

(n=o) 2 a mp 140-142℃
Elemental analysis; (calculated value) C, 59, 12, H, 4, 3
8°N, 4.06. S, 9.29'g < ra: regular direct) C, 59,47, it, 4.33°N, 4.
36. S, 9.50χ IR (KBr); 1773.1710 (C
O) cm-'1390.1356,1188,1175
(SO2)cm-'')l-NMR(CDCl
) :62.32 (3H,s, Ar-ClO
2,93 (2H,t, J=5.37.phth
N-c and 2) 4.29 (2L t, J・5.
37. 2-O-Ts for C) (n・1)1 mutual properties:
Amorphous powder elemental analysis; (calculated value) C, 57, 55, H, 4, 8
3°N, 5.16. S, 11.82χ (observed value)
C, 57, 78,) I, 4.77°N, 4.94.
S, 11.94χIR(KRS); 1775
．． 1710 (Co)cm-'1358.1190,1
175.1155 (SOz)cm-''H-NMR (
CDCJ 3): δ 2.3L2.46 (3H, 3H, s, Ar-C
and: l) 3.43, 3.62 (2H, 28, t, J
=5.86. 2) Ts 3.80 (2H, t, J=5.86.phth for C and 2NC)
Properties of Nc and 2)(n・3)1±: Amorphous powder elemental analysis; (calculated value) C, 56, 39, I, 5.
16°N, 5.98. S, 13.69% (observed value) C, 56, 60, H, 5, 18°N, 5
．． 86. S, 13.56χIR (KBr): 1
775.1710 (Co)cm-'1348.119
0,1178,1158 (SOz)ci-''H-N
MR (CDCl3): δ 2.31.2.42.2.47 (3B, 3HX 2.3H,s, Ar-CII+)
3.35.3.42.3.43.3.46 (2HX 6
．． m, CHzCllz)3.86 (2H,t,
J=5.62. phthNcdant) 4.17 (28
,t, J=5.62+CHZOTs) (n=1)
Properties of 10 b: mp 229-230°C elemental analysis; (calculated value) C, 62,66, H, 4,48°N
, 8.12. S, 6.20χ (observed value) C, 62, 50, H, 4, 47°N, 8.
05. S, 6.20χ IR (KBr); 1770.1705 (Co)c
m-'1330.1150(SOz)am-''H-N
MR (CDCI!3) 2.36 (3H,s, Ar-CH+) 3.72
(2Hx2.t, J=6.IL Cdan,
NCC203, 91 (2) 1x2. t, J・6
．． 11. C! 1zNphth) (n=3) 10
Properties of d: Amorphous powder elemental analysis: (calculated value) C,
59,26,H,4,97°N, 7.68. S,
10.55χ (observed value) C, 59, 46,) 1.5.
03°N, 7.50. S, 10.30χ IR (KBr); 1772.1710 (CO)c
m-'1345, 1155(SO□)cm-''H-N
MR (CDCJ 3): δ 2.3L2.48 (3HX2.3H,s, Ar
-C and 3) 3.45 (2tl x 2.t, J=5
．． 62. phthNctlzcdanKN) Examples 7-1
0.7a (0.67 g) and ↓ (0.37 g) were combined in DMF, reacted with stirring at room temperature for 18 hours, poured into water, and the resulting precipitate was recrystallized from ethanol. 0.623g (99%) is obtained.

Properties of 6a: mp 178479°C elemental analysis;
(Calculated value) C, 59, 29, IL 4.68°N, 8
．． 14. S, 9.3iχ (observed value) C, 59, OL IL 4.72°N, 8
．． 08. S, 9.34χ IR (KBr): 1772.1700 (CO)c
m-'1330, 1150(SOz)ci-''H-
N! 'IR(CDCl:+):δ 2.26
(38,s, 8r-C1l:+)3.33 (2
H, q, J = 5.6L Cl1zNHTs) 3.77
(2+1., t, J=5.61.phthNc
llz)4.96 (IH,t, J=5.6L Cl
1zNHTs) Similarly, (6b), (6c), (6d
) was obtained.

(n・1) 6 properties: elemental analysis of amorphous powder; (
Calculated value) C, 57, 65, H, 5, 03°N, 7
．． 76, S, H, 84χ (observed value) C, 5
7°80. i! , , ), 10°N, 7.56.
S, 11.58χIR (KBr); 1772,
1710 (CO)cz-'1335.1155(S
(h) cm-''+1-N gate R (CDCff 3).

δ 2.36, 2.44 (3!!, 3H, s, A
r-C1h)3.27 (2H,m,C,jizN
IITs) 3.30 (211x2. b-s, CI
IzNCfiz)s 3.89 (2H,t, J=5.37.phthN
cIz)6.74 (In, t, J=5.61
．． N...Ts) (n=2) 1 property: 'mp
198-199.5℃ elemental analysis; (calculated value) C,5
6,89,Ii, 5.18°N,? , 58. S
, 13.02χ (observed value) Cl 56.85 , l]
, 5.20.

N, 7.57. S, 12.93? ! IR (KBr
): 1775. 1710 (CO)cm-
'1343, 1325. 11b2(SOx)cm-
''H-sqR (CDCβ3): δ 2.36. 2.40. 2.45(3)1.3
H, 3)! , s, Ar-CD5) 3.23. 3
．． 40. 3.37 (4H, 2) 1.48. m, NCHzCHzN)3
．． 85 (2H, t, J=6.10.phthNc
HzcHz) 5.22 (IH, t, J=5.61.
N) ITs) (n・3) Properties of 1 Sho: Amorphous powder elemental analysis; (Calculated value) C, 56, 45, 11, 5,
28°N, 7.48. S, 13.70χ (observed value) C, 56, 35,)! , 5.31°N,
? , 33. S, 13.67χ IR (KBr): 1772.1710 (CO)c
m-'1340, 1155(SO2)Cl+1-''+
1-NMR (CDCl 3) 2.31.2.39.2.43.2.47 (3H each,
s, Ar-C)lz) 3.21.3.33.3・42 (2HX7. m, CdanzNc)Iz)s 3.85 (2H,t, phthNC)12)5.
38 (IH, t, NflTs) Examples 11-1
4 6a (1.5g) was dissolved in acetic anhydride (15mt) and acetic acid (3m
f), and add sodium nitrite (0,772
g) (at about 10°C), stirred at this temperature for 1.5 hours, water was added, the resulting crystalline precipitate was collected, washed with water and dried, yielding 1.61g (99%) of yellow crystals 11a. yield)
can get.

Properties of 11a mp 98-100°C (decomposition) elemental analysis; (calculated value) C, 54,6B, H, 4,05°N, 11.26. S, 8.59X (observed value)
C, 54,99,++, 3.97°N, 10.92
．． S, 8.442IR (KBr); 1770
+ 17)8 (Co)cm-'1505 (No)c
m-' 1397, 1380.1360.1195°1163(
SOz)cm-'Others (1l b'), (11C), and (11d) were similarly obtained in good yields. Since nitrosohydrogen 11 is generally unstable, it was used immediately in the next reaction.

11a (1.5g) was dissolved in benzene (60rnl!),
After stirring at 75°C for 24 hours, the solvent was removed and the residue was recrystallized from ethanol to obtain 1.192 g (86% yield) of main 1 (2b), (2C), and (2d) as well. I was caught.

Compounds (2a), (2b), (2C) are Examples 1 to 4
Example 15 Yu (0.73 g) and ↓ (0.49 g, 1 equivalent DMF
(The suspended precipitate disappears when the mixture is mixed with 20 ml of water and stirred at about 60°C. After another hour of reaction, the reaction solution is poured into 400 ml of water containing salt. The resulting precipitate is collected, and chloroform moon (95:5 v/ v) was developed and subjected to silica chromatography, la was 0.40 (60% yield) and 1
0.12 g (13% yield) can be obtained.

Pressure removal Properties of top 1: Earthworks contain known substances (CheIIl
, Lott, 1)), but 'II
-NMR is reported. Since there is no one, I will write it below.

) l-NMR (CDC13): 63.
62 (28,t, J=6.83. -Cdan, -
Br) (2d) 4.12 (2H,t
, J-6,83,I)hthN-CHz-).
1 Soil properties: Identified as shown in Example 2.

Example 16) was mixed with 5 (4.5 g) and ↓ (3.0 g, 1 equivalent) in DMF for 1 hour (60 mA+), and about 7
Stir for 12 hours at 5°C, and pour the reaction solution into water containing salt (note 1 to 600 ml). The resulting precipitate is collected, dried, and recrystallized from ethanol with acetate.
5.255 g (97% yield) of 6a are obtained.

Properties of 4g 6a: Identified as shown in Example 7.

Example 17 13 (m=3) 6c12b (0,
72g) and metallic sodium (23mg).

1.6 equivalents) was obtained by prior treatment in ethanol (20 ml). 12b sodium salt in DMF (2
' Om (1) and add DMF (5 ml
2a (0.22 g 11 eq.) dissolved in ) is added dropwise at room temperature. After the reaction was stirred for 20 hours, it was poured into water, the resulting oil was collected, and subjected to silica gel chromatography.
/v), the corresponding 13 (m=3) becomes 15
mg (2.6%) and 230 mg (49%) of 6c.

Compound α-to is the compound (10d) (n) obtained in Example 6.
=3). Compound (6c) was identified as the compound (6c) obtained in Example 9.

Compounds (6a), (6b), (6d) and compound (13) (m=9) were obtained in the same manner. The properties of compound (6a) were the same as those of Example 7, and the properties of compounds (6b) and (6d) were the same as those of Examples 8 and 10, respectively.

Properties of compound am (m=9): Amorphous powder IR (KBr
); No absorption of N)l 1775, 1710 (CO
)cm-'1342.1155<SO2)cm-' was identified as -13 (m=9).

The results of the above examples are summarized in the following table.

Written amendment (method) % formula % 1. Indication of case 1985 patent application No. 209029
No. 3. Relationship with the person making the amendment Applicant name (679) RIKEN 4, Agent

Claims (5)

[Claims] (1) N-phthalimide derivative represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer from 0 to 7, Phth is a phthaloyl group,
T_s represents a tosyl group, and X represents O or NH. ) (2) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, n is an integer from 0 to 3, T_s is a tosyl group, X is O
Alternatively, NH and Y represent a bromine atom or OT_s. ) and the compound (I) represented by PhthN^-M^+(
Phth represents a phthaloyl group, and M represents an alkali metal atom. ) A method for producing an N-phthalimide derivative represented by the following general formula, characterized by reacting the compound represented by: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (3) General formula (6) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer from 0 to 3, Phth is a phthaloyl group,
T_s represents a tosyl group. ) is N-nitrosated to obtain a compound represented by the general formula (II) ▲Mathical formula, chemical formula, table, etc.▼, and the general method is characterized by treating the compound in benzene. A method for producing N-phthalimide derivatives represented by formula (2) ▲ Numerical formulas, chemical formulas, tables, etc. are available. (4) General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer from 0 to 3, Phth is a phthaloyl group,
T_s represents a tosyl group. ) is reacted with a compound represented by the general formula (12) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, m represents an integer from 0 to 3.) A method for producing N-phthalimide derivatives represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, l is m+n+1.) (5) General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer from 0 to 7, Phth is a phthaloyl group,
T_s represents a tosyl group. ) is reacted with a compound represented by the general formula (12) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, m represents an integer from 0 to 3.) A method for producing polyamines expressed by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, l is m+2n+2.)