JPS63104987A - Porphyrin-germanium complex and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1-R3 represent OH, 1-3C alkoxyl or O(CH2CH2O)n H (n is 2-6); X and Y represent OH, alkoxyl OCOCH3 of halogen atom; when any one or more of R1-R3 represent OH or O(CH2CH2O)nH, residues formed by eliminating H from at least one of those groups in other molecules may be at least one of X and Y] or intermolecular complex thereof. EXAMPLE:Bismethoxy-7,12-bis( 1-( 2-( 2-hydroxyethyloxy)ethyloxy)ethyl)-3,8,13,17- tetramethyl-2,13-bis(2-(2-(2-hydroxyethyloxy-)ethyloxy)carbonyl-ethyl) porphinato germanium (IV). USE:For diagnosis and remedy of cancer. PREPARATION:A porphyrin-germanium complex expressed by formula II (R represents OH or 1-3C alkoxyl; X' and Y' represent X and Y) is treated with an acid and then treated with water or a water-containing acid.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel porphyrin-germanium complex used for diagnosis and treatment of cancer and a method for producing the same.

(Prior Art) Recently, porphyrin derivatives that have an affinity for cancer cells and have a photosensitizing effect have been used in combination with laser light irradiation to achieve results in the diagnosis and treatment of cancer (T,
J. Doughherty, “Photodyn.
a-mic Therapy of Tumors
and 0ther Diseases”26.7～2
79 pages (1985)]. Hematoporphyrin (hereinafter abbreviated as HP) or hematoporphyrin derivatives (hereinafter abbreviated as HPD) are mainly used in this trap, but the former is difficult to obtain in pure form [R, ni, DiNello et al., “The Porphyrin
s” Volume 1, pp. 297-298 (1978): The latter is acetylated and then treated with alkali and acid, and is a mixture of dozens of porphyrin derivatives. This has become a big problem.

Regarding the germanium complex of porphyrin, the present inventors have developed a protoporphyrin germanium complex (Japanese Unexamined Patent Publication No. 1985-11985, 1983-1989), which is the raw material for the compound of the present invention.
31688) was synthesized.

Recently, hydroxyl group,
Alternatively, germanium complexes of porphyrin derivatives having ether groups have been reported, but there are problems with the reaction method.

(Problems to be solved by the invention) HP currently being used for cancer diagnosis and treatment
As mentioned above, D can only be obtained as a mixture of several dozen types,
The structures of many of its constituent components have not been confirmed. Therefore, K for clinical use is a major hindrance in terms of determining toxicity and ensuring a certain level of quality. In order to solve this problem, it is important to obtain a pure compound that has the ability to accumulate in cancer cells for diagnosis and has a photosensitizing effect for treatment.

A conventional example of synthesizing a germanium complex of a porphyrin derivative having a hydroxyl group or an ether group (JP-A-6
1-83185), the porphyrin derivative is directly reacted with germanium tetrachloride in pyridine at high temperature, which poses a synthetic problem. In reality, dehydration and dealcoholization occur and the desired compound cannot be obtained.

(Means for solving the problem) The present inventors succeeded in synthesizing a new porphyrin-germanium complex having a hydroxyl group or an ether group in the side chain by chemically modifying the vinyl group of the protoporphyrin-germanium complex. The present invention was completed by obtaining a compound that has photosensitizing action and the ability to accumulate in cancer tissues.

The present invention is based on the general formula [wherein ul l R2 and R8 are each independently a hydroxyl group, a cl-c3 alkoxy group, or 0(CH2CH2
0) nH (where n represents an integer of 2 to 6), X and Y each independently represent a hydroxyl group, an alkoxy group, an OCOC
Indicates H3 or halogen. However, Jul.

One or more of R2 and R3 is a hydroxyl group or 0 (
CH2CH20)nH, the residue obtained by removing hydrogen from at least one of these groups in another molecule may be at least one of X and Y. ] A porphyrin-germanium complex or an intermolecular complex thereof,
and its manufacturing method.

The synthetic route of the porphyrin-germanium complex of the present invention is briefly as follows.

That is, a compound represented by the general formula CII is treated with an acid and then treated with water or with an acid containing water to obtain a compound represented by the general formula [■]. Examples of acids used in this reaction include hydrogen bromide-acid mixture and sulfuric acid. 20 when using 30% hydrogen bromide acetic acid solution
The reaction is preferably carried out at ~30°C for about 24 hours, and the subsequent reaction with water is preferably carried out at a low temperature, usually -5~30°C.
Do this for about 1 hour at 10°.

Adding an acid to the compound represented by the general formula [■] with the general formula RIH
(In the formula, R1 is an alkoxy group of 01 to C3 or 0(CH
2CH20) nu (n is an integer of 2 to 6). ) A reaction reagent added to the compound represented by formula (■) is reacted to obtain a compound represented by general formula [■].

As the acid used in this reaction, those normally used for esterification or etherification can be used, such as hydrogen chloride and sulfuric acid, but sulfuric acid is preferably used. The reaction with this reagent is completed in 5 minutes to 120 hours at -20°C to 100°C, and etherification can be suppressed by keeping it at a lower temperature for a shorter time.
The reaction is preferably carried out at 0°C for about 30 minutes to 5 hours.

After treating the compound represented by the general formula [E] with an acetic acid solution of hydrogen bromide, the compound represented by the general formula R1■ (where hole 1 in the formula has the same meaning as above)
When reacted with a compound represented by the formula CID, a compound represented by the general formula CID is obtained. The concentration of the hydrogen bromide acetic acid solution used here is not particularly limited, but it is usually preferably 30%, and the reaction is completed in 1 to 120 hours at 0 to 100°C, but usually about 24 hours at 20 to 30°C. The reaction is preferred. The reaction with RH is completed in 5 minutes to 5 hours at 0 to 150°C, but it is usually preferable to react at around 80°C for about 3 hours.

The compound represented by the general formula CID is obtained by hydrolyzing the compound represented by the general formula [I11] and [■] using an acid or an alkali in a conventional manner. The acid usually used for hydrolysis is, for example, a widening acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid or p-toluenesulfonic acid, and the alkali is sodium hydroxide,
Potassium hydroxide, ammonia, etc. are used, but sodium hydroxide is preferably used. This reaction is 0-150
The reaction is completed in 5 minutes to 48 hours at <RTIgt;C,</RTI> but for example, the reaction using sodium hydroxide in methanol is completed in 4 hours under reflux.

Purification of these novel porphyrin-germanium complexes after the reaction is carried out by conventional methods such as extraction, recrystallization, chromatography, etc. When positional isomers exist, it is usually not necessary to separate them, but each isomer can also be isolated by HPLC or the like.

A hydroxyl group, 0(OH2CH20)nu, is present in the resulting complex.

When a carboxyl group is present, a complex residue obtained by removing at least one terminal hydrogen from these groups can coordinate to Ge of another complex molecule to form an intermolecular donor. In this case, the above complex residue becomes X or (and) Y of another complex molecule.

Since intermolecular borrowing bodies tend to be easily formed, for example, by heating, they may also be produced during the purification process.

(Example) The present invention will be further explained below in the form of examples.

Example 1 Bispromorph, 12-jetinyl-3,8°13.1
The mixture was poured into 7-tetramethyl-2,18-bis(2-methoxycarbonylethyl)porphinato gel and stirred for 1 hour. After adjusting the pH to 8 to 4 with a concentrated aqueous sodium hydroxide solution, 55 m7 of a mixture of dithyl acetate and acetic acid (10:1) was added.
The organic layer was collected and concentrated to dryness under reduced pressure to give a solution of 0.7
A crude product of bisacetyloxy-7,12-bis(1-hydroxyethyl)-3,8,18,17-natramethyl-2,18-bis(2-carboxyethyl)porphinatogermanium (IV) was obtained. .

IR(KBr)cm, 2965.2920.286
5.

2815.1720 This was dissolved in methanol tomz, an ether solution of diazomethane prepared from 1 g of nitrosomethylurea was added, and after 15 minutes, the solvent was distilled off, and the residue was dissolved in chloroform and a chloroform-pyridine mixture (50: 1 to 4: 1)
The product is purified by column chromatography using alumina (activity ■) as an eluent and alumina (activity ■) as a packing material, and the main distillate is concentrated to dryness under reduced pressure.

The residue was dissolved in 10 mJ of 1% sodium hydroxide in methanol.
After refluxing for 4 hours, the solution was concentrated to dryness under reduced pressure. Add 5 ml of water to the residue! Add acetic acid to adjust the pH to 8-4, collect the resulting crystals, and add 0.5 ji of bisacetyloxy-7,12-bis(1-hydroxyethyl)-3,8.
, 13,17-tetramethyl-2,18-bis(2-carboxyethyl)porphinatogermanium (■) was obtained.

1 liter (KBr) cm, 8420, 2965, 292
0°2865.2815.1720.

1B85.1865.1130.

1080.950.840.

730.610 Visible absorption spectrum (PBS) nm: 401.

582.569.5 N input fR (CDaOD) δ; 2.22(d),
3.60(S), 8.74(broad), 4
．． 50(t), 4.70(s).

10.30 (S), 10.46 (S).

10.66 (S), t 0.75 (s) Example 2 Bispromorph, 12-jetinyl-3,8゜1(,1
7-Tetramethyl-2,18-bis(2-methoxycarbonylethyl)porphinatogermanium(IV) 4
．． Add 120 mj' of an 80% acetic acid solution of hydrogen bromide to 9 and stir at room temperature for 24 hours, then pour into 400 mJ of ice water and stir for 1 hour. This was adjusted to pH 3 to 4 with a concentrated sodium hydroxide aqueous solution and then mixed with ethyl acetate-acetic acid (10:1).
The mixture was extracted four times with 220 mJ, and the organic layer was collected and concentrated to dryness under reduced pressure. The residue was dissolved in 5% sulfuric acid in methanol at 240 ml.
After dissolving in mj' and leaving at room temperature for 10 hours, 250 mJ of chloroform and 250 mJ of water were added for extraction, and the chloroform layer was washed four times with 250 mJ of water. The chloroform layer was dried over anhydrous magnesium sulfate and then concentrated to dryness under reduced pressure. The residue was subjected to column chromatography using chloroform and a chloroform-pyridine mixture (50:1 to 4:1) as the eluent and alumina (activity: ■) as the packing material. Separate into 3 eluates.

The first eluate was concentrated to dryness under reduced pressure, and a reddish-brown bishydroxy-7,12-bis(1-methoxyethyl)-3,
8,13,17-natramethyl-2,18-bis(2-
0.89 of methoxycarbonylethyl)porphinatogermanium (IV) was obtained.

Visible absorption spectrum k (CHCj?a) nm;
4 Q 8゜587.578.5 IR (KBr) cm, 2960, 2910, 28
50°2810.173O NMR (CFaCO2D) δ: 10.79, 10.7
6, 10.4210.38 (S, 4H), 6.12 (q, 2H), 4.53 (t, 4I().

8.81.3.76 (S, 12H).

3.76 (S, 6H), 8.70.

3.68(S, 6I(), i40°8.88(t, 4H), 2.30(d,
The second eluate of 6H), -7,5(S, 2I() was concentrated to dryness under reduced pressure to give reddish brown bishydroxy-7().
or12)-(1-methoxyethyl)-12(OF2)
1.8 g of -(1-hydroxyethyl)-3,8,18,17-natramethyl-2°18-bis(2-methoxycarbonylethyl)porfinatogermanium (N) was obtained.

Visible absorption spectrum (cucz 3 ) nm;
407.5537.572.5 IR (KBr) cm, 2960, 2940, 291
0°2860.28 L (1,1735 NMR(CF 3 CO2D ) δ; 10.89
, 10.83.

10.68, 10.59 (S, 41° 7.94 (Q, 2H), 4.73 (t.

4H), 4.08 (, S, 811i).

4.01, 3.88 (S, 12H).

3.74, 3.72 (S, 6H).

3.54 (t, 4I-I), 2.60 (d
.

6H) The third eluate was concentrated to dryness under reduced pressure to give a reddish-brown bishydroxy-7,12-bis(1-hydroxyethyl)-8
,8,13,17-tetramethyl-2,18-bis(2
-Methoxycarbonylethyl)porphinatogermanium (IV) 0.7.9 was obtained.

IR (KBr) cm, 2960, 2940, 291
0°2850.1735 NMR (CFaC02D) δ; 10.87, 10.82
゜10.66.10.57 (S, 4I ().

7.92 (q, 2H), 4.72 (t.

4I (), 4.00, 3.88 (S.

12H), 3.74, 3.71 (S.

6I (), 3.68 (t, 4H).

2.59(d,6H) Example 3 Bishydroxy-7,12-bis(1-
methoxyethyl)-3,8,13,17-tetramethyl-2,18-bis(2-methoxycarbonylethyl)porphinatogermanium (■) 0,5! i was dissolved in 10 mJ of a 1% methanol solution of sodium hydroxide, refluxed for 4 hours, and then concentrated to dryness under reduced pressure. 5 methanol to the residue
ml! , 0.2 g of sodium hydrogen carbonate was added and refluxed for 30 minutes. After cooling, the white solid was removed and the p solution was concentrated to dryness under reduced pressure to give a reddish brown bismethoxy-7,12-bis(1-methoxyethyl)-3. ,8,13,17-natramethyl-2
．． 0.4 g of 18-bis(2-carboxyethyl)porphinatogermanium (IV) disodium salt was obtained.

Visible absorption spectrum (CH30H) nm; 404
．． 8.

584.5, 570.5 IR (KBr) cm; 2970, 2920, 286
0゜2810.1560,1405 NMR (CD30D) δ; 10.92, 10.85, 1
0.72°10.56 (S, 4H), 6.2
5(q, 2H), 4.61(t, 4H).

8.87, 3.81 (S, 12H).

3.65 (S, 6H), 3.2 (t).

4H), 2.31(d, 6H).

-2,99(S, 6LI) Example 4 Bishydroxy-7(OrL2)-(1
-methoxyethyl)-12(OF2)-(1-hydroxyethyl)-3,8,13,17-tetramethyl-2,
0.5y of 18-bis(2-methoxycarbonylethyl)porphinatogermanium (■) was treated in the same manner as in Example 2 to obtain reddish-brown bismethoxy-7 (or 12).
-(1-methoxyethyl)-12(OF2)-(1
0.4 g of 3,8,13.17-natramethyl-2°18-bis(2-carboxyethyl)porphinatogermanium (IV) disodium salt was obtained.

Visible absorption spectrum (CHIIOR) nm: 40
4.

534.5, 570.5 1R (KBr) cm; 2960, 2910, 285
0°2800.1570.1405 NMR (CD30D) δ; 10.97.10.93,
10.85.

10.71, 10.55 (S, 4I ().

6.74.6.25 (q, 2H).

4.62 (t, 4H), 3.86 (S).

12H), 3.68 (S, 3H).

8.2 (t, 4H), 2.34 (d.

6H), -8,02(S, 6II) Example 5 Bishydroxy-7,12-bis(1-
hydroxyethyl)-3,8,18゜17-tetramethyl-2,18-bis(2-methoxycarbonylethyl)
Porphinatogermanium (IV) 0.5, F was treated in the same manner as in Example 1, and a reddish-brown bismethoxy-
7,12-bis(1-hydroxyethyl)-3,8,1
0.3y of 3,17-tetramethyl-2,18-bis(2-carboxyethyl)porphinatogermanium(IV) disodium salt was obtained.

Visible absorption spectrum (CH30H) nm: 40
8.8 +584.5,570.5 IR (KBr) cm, 2950,2910,2
850°2800.1570.1405 NΔ1R(CD30D)δ;11.0. L0.7,10
．． 52 (S.

4H), 6.71 (Q, 2H).

4.6(t, 4I(), 3.84(S.

12H), 8.2 (t, 4H).

2.82 (d, 6H), -3,04 (s,
6H) Example 6 Bishydroxy-7,12-bis(1-
hydroxyethyl)-3,8,13゜17-tetramethyl-2,18-bis(2-methoxycarbonylethyl)
0.1E of 7,12-bis(
An intermolecular compound of 1-hydroxyethyl)-8,8,18,17-natramethyl-2゜18-bis(2-methoxycarbonylethyl)porphinatogermanium (IV) was obtained.

IR (KBr) cm-'; 2960, 2940
, 2910.

2850.1735 NMR (CDCJ3) δ; 11-10 (broad
)5~4.2 (broad) 4.2~3 (broad) 3~2' (broad) NMR (CFaO02D) δ: 10.87.108
2.

10.66.10.57 (s, 4H).

7.92 (Q, 2H), 4.72 (t.

4H), 4.00.3.88 (S.

12Zf), 3.74, 171 (S.

6H), 3.63 (t, 4I().

2.59(d,6H) Example 7 Bishydroxy-7(Or12)- obtained in Example 2
(1-methoxyethyl)-12(or7)-(1-hydroxyethyl)-1,8,13゜17-tetramethyl-
2,18-bis(2-methoxycarbonylethyl)porphinatogermanium(IV) 0.1.9 in Example 6
Heat in the same manner as 0. II 7(or12)-(1-methoxyethyl)-12(or7)-(1-hydroxyethyl'')-3+8+13.17-tetramethyl-2,1
An intermolecular complex of 8-bis(2-methoxycarbonylethyl)porphinatogermanium (IT) was obtained.

NMR (CDCJ3) δ: 11-10.3 (
broad, 4H).

6, 5 5 (broad, 2 H) +5-4.
4 (broad, 4H) +4.4-3.6
(broad, 21 H).

8.6-8J (broad, 4H).

8-2 (broad, 6H) Example 8 Bispromorph, 12-jetinyl-3,8°13.1
7-Tetramethyl-2,18-bis(2-methoxycarbonylethyl)porphinatogermanium(IV) 1
．． Add 50 mJ of a 30% acetic acid solution of hydrogen bromide to 9 and stir at room temperature for 24 hours, then concentrate to dryness under reduced pressure, add 30 mJ of diethylene glycol to the residue, and stir at 80°C for 3 hours. After cooling, the mixture was diluted with methylene chloride ao o mz and extracted with 600 mj' of water. The aqueous layer is saturated with sodium chloride, extracted with methylene chloride aoomz, the organic layer is dried over anhydrous magnesium sulfate, and the solvent is distilled off. The residue was purified by column chromatography using alumina (activity ■) as a packing material and methylene chloride-methanol as an eluent to obtain 0.51 bismethoxy-7゜12-bis(1
-(2-(2-hydroxyethyloxy)ethyloxy)ethyl)-3,8,13゜17-tetramethyl-2,
18-bis(2-(2'-(2-hydroxyethyloxy)ethyloxy)carbonylethyl)porphinatogermanium (IV) was obtained.

Visible absorption spectrum (cncza) nm; 41
4.

541.5,577.5 Example 9 Bismethoxy-7,12-bis(1-(
2-(2-hydroxyethyloxy)ethyloxy)ethyl)-3,8,13,17-tetramethyl-2,18
-bis(2-(2-(2-hydroxyethyloxy)ethyloxy)carbonylethyl)borfui 1-1-/
Flua='hum (IY) 50my and sodium hydroxide 34m, 9 were dissolved in 5ml of methanol and refluxed for 4 hours, then the solvent was distilled off and the residue was dissolved in 0.5ml of water! dissolve in Sephadex 010 after adding 0.05 mJ of acetic acid
The reddish-orange eluate was collected, the water was distilled off under reduced pressure, and 50 mJ7 of bishydroxy-
7,12-bis(1-(2-(2-hydroxyethyloxy)ethyloxy)ethyl)-1,8,13,17-
Tetramethyl-2,18-bis(2-carboxyethyl)porphinatogermanium (IY) was obtained.

Visible absorption spectrum (H2O) nm; 402
, 533° Example 10 Bismethoxy-7,12-bis(1-(
2-(2-hydroxyethyloxy)ethyloxy)ethyl)-3,8,13,17-tetramethyl-2,18
-Bis(2-(2-(2-hydroxyethyloxy)ethyloxy)carbonylethyl)porphinatogermanium (IV) 0.11 is heated under reduced pressure using a rotary evaporator at an external temperature of about 60°C for 4 hours. 0.1 g of 7,12-bis(1-(2-(2-hydroxyethyloxy)ethyloxy)ethyl)-3,8°13.17-tetramethyl-2,18-bis(2-(2-hydroxyethyloxy)ethyloxy)ethyl)
-(2-Hydroxyethyloxy)ethyloxy)carbonylethyl)porphinatogermanium (N) was obtained.

NMR (CD(,/3)δ; 10.8-10.6
, 10.3-10, l (broad, 4H),
6.2-5.9 (broad, 2H), 4
．． 6-4.2 (broad, 4 El), 4
-3.6 (broad), 8.8-3.5 (br
oad).

3, 5-2.5 (broad), 2.2 B (b
road, d, 6H), 0.9-0.3(bro
ad), 0--0.3 (broad).

-0,8--0,7(broad) (Effects of the Invention) The compound of the present invention shows the ability to accumulate in cancer cells, and emits fluorescence when stimulated with light. Furthermore, by irradiating it with light in the presence of oxygen, heavyt oxygen is generated, and this heavyt oxygen has a cancer cell killing effect. Because of these actions, the compounds of the present invention can be said to be useful compounds for the diagnosis and treatment of cancer.

Claims (5)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc.
2CH_2O)_nH (where n represents an integer of 2 to 6), and X and Y each independently represent a hydroxyl group, an alkoxy group, OCOCH_3, or a halogen. however,
When any one or more of R_1, R_2 and R_3 is a hydroxyl group or O(CH_2CH_2O)_nH, the residue obtained by removing hydrogen from at least one of those groups in another molecule is at least one of X and Y. It may be one. ] Porphyrin-germanium complex or its intermolecular complex. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, two R are independently hydroxyl groups or C_1~
The alkoxy group of C_3, X' and Y' are each independently a hydroxyl group, an alkoxy group of C_1 to C_3, OCOCH
_3 or halogen) is treated with an acid, and then treated with water or with an acid containing water,
General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X and Y have the same meanings as X' and Y' above. However, at least one of A method for producing a porphyrin-germanium complex or an intermolecular complex thereof, which is represented by (both may be a residue obtained by removing hydrogen from one of them). (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X and Y are each independently a hydroxyl group, C_1 to C
_3 Indicates an alkoxy group, OCOCH_3 or halogen. However, at least one of X and Y may be a residue obtained by removing hydrogen from at least one of a hydroxyl group and a carboxyl group in another molecule. ), or its intermolecular complex, is combined with an acid and the general formula R.
^1H [In the formula, R^1 represents an alkoxy group of C_1 to C_3 or O(CH_2CH_2O)_nH (n is an integer of 2 to 6). ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reaction with a reaction reagent consisting of a compound represented by [In the formula, R_1 and R_2 are independently hydroxyl group, C
_1 to C_3 alkoxy group or O(CH_2CH_2O)_nH (n is an integer of 2 to 6. The same applies hereinafter), R_3 is C_1 to C_3 alkoxy group or O(CH_2CH_2O)_nH, X and Y
independently represent a hydroxyl group, a C_1 to C_3 alkoxy group, OCOCH_3, or a halogen. However, R_
1. If any one or more of R_2 and R_3 is a hydroxyl group or O(CH_2CH_2O)_nH, the residue obtained by removing hydrogen from at least one of those groups in another molecule is at least one of X and Y. It may be one. ]
A method for producing a porphyrin-germanium complex or an intermolecular complex thereof. (4) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, two R are independently hydroxyl groups or C_1~
The alkoxy group of C_3, X and Y are each independently a hydroxyl group, the alkoxy group of C_1 to C_3, OCOCH_3
Or indicates halogen. ) is a porphyrin represented by
After treating the germanium complex with an acetic acid solution of hydrogen bromide,
General formula R^1H [wherein R^1 is a C_1 to C_3 alkoxy group or O(CH_2CH_2O)_nH (n is 2
~6 integer). ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting with a compound represented by [In the formula, each R^1 is independently a C_1 to C_3 alkoxy group or O (CH_2CH_2O) _nH (n is an integer of 2 to 6), and X and Y are as defined above. However, when R^1 is O(CH_2CH_2O)_nH, the residue obtained by removing hydrogen from at least one of the groups in another molecule may be at least one of X and Y. ]
A method for producing a porphyrin-germanium complex or an intermolecular complex thereof. (5) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are independently hydroxyl group, C
_1 to C_3 alkoxy group or O(CH_2CH_2O)_nH (n is an integer of 2 to 6. The same applies hereinafter), R^3 is C_1 to C_3 alkoxy group or O(CH_2CH_2O)_nH, X and Y
independently represent a hydroxyl group, a C_1 to C_3 alkoxy group, OCOCH_3, or a halogen. However, R^
1. If any one or more of R^2 and R^3 is a hydroxyl group or O(CH_2CH_2O)_nH, the residue obtained by removing hydrogen from at least one of those groups in another molecule is X and Y The general formula ▲ mathematical formula, chemical formula, table, etc. is characterized by hydrolyzing a porphyrin germanium complex or an intermolecular complex thereof in the presence of an acid or an alkali. Yes▼ (In the formula, R^1 and R^2 have the same meanings as above, X and Y
independently represent a hydroxyl group, a C_1 to C_3 alkoxy group, OCOCH_3, or a halogen. However, at least one of X and Y is a carboxyl group of another molecule, or when one or more of R^1 and R^2 is a hydroxyl group or O(CH_2CH_2O)_nH, at least one of those groups It may be a residue excluding hydrogen]
A method for producing a porphyrin-germanium complex or an intermolecular complex thereof.