JP2752376B2 - New porphyrin compounds - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel porphyrin compound. The porphyrin compound of the present invention has polymerizability, and the polymer obtained by polymerizing the porphyrin compound of the present invention is useful as an oxygen carrier material, a recording material, a photochemical hole burning material or a magnetic material.

(Prior art) With respect to polymerizable porphyrin compounds, many researches and developments have been carried out in view of interest from a biochemical or quantum chemical viewpoint and expectations for many industrial applications. (1) Journal of Polymer Science (Polymer Chemistry Edition), 19 1109 (19)
81) (2) Journal of Polymer Science (Polymer Letter Edition), 21 693 (1983) (3) Porphyrin Chemistry (by Tetsuro Naga et al., Kyoritsu Shuppan, 1982), p.3 And so on.

(Problems to be Solved by the Invention) Among the polymerizable porphyrin compounds described in these documents, some are difficult to synthesize, and some have low polymerizability even if they can be synthesized. In addition, some polymers can be obtained only by a mixture containing a polyfunctional porphyrin compound, so that a polymer obtained by polymerization is unlikely to be linear.In any case, a conventional porphyrin compound has a problem in that a polymer is obtained. It is hardly satisfactory.

Accordingly, an object of the present invention is to provide a novel polymerizable porphyrin compound.

(Means for Solving the Problems) According to the present invention, the above object is achieved by a general formula [Wherein, R ^a , R ^b and R ^c each represent a hydrogen atom or a lower alkyl group; (R ^d represents a lower alkyl group), -S-, ( ^Re represents a hydrogen atom or a lower alkyl group) and represents one group selected from the group consisting of: Y represents an alkylidene group having 1 to 5 carbon atoms, or -O-, (R ^f represents a hydrogen atom or a lower alkyl group), (R ^g represents a hydrogen atom or a lower alkyl group).
And Z represents -O- or And r represents 0 or 1, when r is 0, s represents 0 or 1, and t represents 1, when r is 1, s represents 1, and t represents 0 or 1. And P is (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
^10, one of among R ¹¹ and R ¹² are defined or below represents a bond ^{R 1, R 2, R 3} , R 4, R 5, R 6, R
^{7, R 8, R 9,} R 10, R 11 or one of radicals represented by R ¹²
R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a phenyl group which may have a lower alkyl group or a hydroxyl group as a substituent, or a lower alkyl group as a substituent. Represents a pyridyl group which may have R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may each have a hydrogen atom or a hydroxyl or lower alkoxycarbonyl group as a substituent. Represents a certain lower alkyl group, and M represents a metal group).

In the general formula [I], R ^a , R ^b and R ^c each represent a hydrogen atom or a lower alkyl group, and examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group and an isobutyl group. Can be Among the compounds represented by the general formula [I], the compounds represented by R ^a and R ^b each representing a hydrogen atom and R ^c representing a hydrogen atom or a methyl group are polymerizable (polymerization rate, degree of polymerization). It is preferable from the point of view.

In the general formula [I], X is (R ^d represents a lower alkyl group), -S-, (R ^e represents a hydrogen atom or a lower alkyl group) represent one group selected from the group consisting of, as the lower alkyl group as R ^d and R ^e, a methyl group, an ethyl group, a propyl group, n- butyl And isobutyl groups.
The compound represented by the general formula [I] includes a compound having a group represented by X (r: 1) and a compound having no group represented by X (r: 0). A compound having no group represented by X, and X is The compounds [(meth) acrylate derivatives, vinyl ester derivatives, vinyl ether derivatives, (meth) acrylamide derivatives, styrene derivatives] represented by the following formulas are preferred.

Y is an alkylidene group having 1 to 5 carbon atoms, or -O-, (R ^f represents a hydrogen atom or a lower alkyl group) (R ^g represents a hydrogen atom or a lower alkyl group).
Represents an alkylene group. -CH ₂ as the alkylidene group
−, Examples of the lower alkyl group for R ^f and R ^g include a methyl group, an ethyl group, a propyl group, an n-butyl group, and an isobutyl group. Examples of the alkylene group include -CH ₂ CH ₂ -and -CH ₂ CH ₂ CH ₂ CH ₂ −, —CH ₂ OCH ₂ —, CH ₂ CH ₂ O _k CH ₂ CH ₂ — (k represents an integer of 1 to 9), CH ₂ CH ₂ CH ₂ CH ₂ O ₁ CH ₂ CH ₂ CH ₂ CH ₂ — ( l represents an integer of 1 to 4), (M represents an integer of 1 to 4), (N represents an integer of _{1~4), CH 2 CH 2 NH} p CH 2 CH 2 -
(P represents an integer of 1 to 9), CH ₂ CH ₂ S _q CH ₂ CH ₂ — (q represents an integer of 1 to 9), And the like.

As described above, the compound represented by the general formula [I] has X
There are compounds having a group represented by and compounds not having a group, and compounds having no group represented by X may have a group represented by Y (s: 1) or may not have a group represented by (s:
0). The compound having a group represented by X has a group represented by Y (s: 1).

In the general formula [I], Z is -O- or Wherein a compound having no group represented by X has a group represented by Z (t: 1), and a compound having a group represented by X may have a group represented by Z ( t: 1),
It may not have it (t: 0).

In the group P represented by the formula [II], R ¹ , R ² ,
R ³ and R ⁴ each represent a phenyl group which may have a lower alkyl group or a hydroxyl group as a substituent, And pyridyl groups which may have a lower alkyl group as a substituent and are each represented by R ¹ , R ² , R ³ and R ^4. And the like. Further, in the group P represented by the above formula [II], R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R
¹² represents respectively, the lower alkyl group it may have a hydroxyl group or a lower alkoxycarbonyl group as a _{substituent, -CH 3, -C 2 H 5} , -C 4 H 9, -CH 2 CH 2 COOCH 3,
_{-CH 2 COOCH 3, -CH 2 CH} 2 COOC 4 H 9, -CH 2 CH 2 OH , and the like.

In the formula [II], M represents a metal capable of forming a metal complex with the porphyrins, and is preferably one having no polymerization inhibition or polymerization inhibition. Illustrating such metals are Zn, Cu, Ni, Co, F
e, Mn, Ag, In, V, Hg, Tl, Sn, Pt, Ir, Mg, Ca, Sr, Ba, Cd, Si, Ge, R
n, Pb, Au, As, Sb, Bi, Sc, Al, Ga, Cr, Mo, Ti, Zr, Hf, Eu, Pr, Yb,
Y, Th, Ta, W, Re, Os, Nb, Pd, Er and the like.

These metals may form complexes with porphyrin and combine with oxygen, sulfur, nitrogen and the like.

The compounds represented by the general formula [I] are exemplified in Table 1.

^{P 1, P 2, P 3} , P 4, P 5, P 6 and P ⁷ in Table 1 means the following, respectively.

The compound represented by the general formula [I] can be produced, for example, by a reaction represented by the following formula (1), (2), (3) or (4).

[Wherein, R ^a , R ^b , R ^c , X, Y, Z and P are the same as above, t ′ represents 0 or 1, X represents —O—, (R ^d is as defined above) or -S-, A ¹ represents a lower alkyl group, and A ² represents a hydroxyl group, and X represents ( ^Re is the same as defined above), A ¹ and A ² are selected from a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group and a toluenesulfonyloxy group, provided that they are selected to react with each other. Represents one group selected from the group consisting of [Wherein R ^a , R ^b , R ^c , X, Y, Z, P and r are the same as above, and A ³ and A ⁴ are selected so as to react with each other. ³ represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group or a toluenesulfonyloxy group, and A ⁴ represents -CHO, -CH ₂ OH, -COOH,
_{-CH 2 Cl, -CH 2 Br,} -CH 2 I, —COCl, —COBr, —CH ₂ NR ^h H (R ^h represents a hydrogen atom or a lower alkyl group) or —OH. (Wherein, R ^a , R ^b , R ^c and P are the same as described above, and R ⁱ represents a lower alkyl group having 1 to 4 carbon atoms) (In the formula, R ^a , R ^b , R ^c and P are the same as above, and R ^j represents a lower alkyl group.) The details of the reaction conditions in these reactions differ depending on the synthesis reaction selected, but In the case of the reaction represented by the formula (1) or (2), using a basic catalyst such as a tertiary amine,
Compound (III) or (III) ′ is reacted with compound (IV) or (IV) ′ in an inert solvent such as chloroform at a temperature of −50 to 150 ° C. for 1 to 100 hours to obtain a compound represented by the general formula [I]: Thus, a crude compound of porphyrin represented by the following formula is obtained.
The desired porphyrin compound can be obtained by separating and purifying this by a conventional method using column chromatography. Further, in the case of the reaction represented by the formula (3) or (4), the compound (V) or (V) ′ and the compound (VI) or (VI) ′ are reacted with mercury acetate as a catalyst such as chloroform. By reacting in an inert solvent at a temperature of -50 to 150 ° C for 1 to 20 hours, a crude porphyrin compound represented by the general formula [I] is obtained. Then, the desired porphyrin compound can be obtained by separation and purification by a conventional method using column chromatography.

The compound represented by the general formula [I] has vinyl polymerizability, and gives a polymer having a porphyrin ring in a side chain by homopolymerization or copolymerization. For the polymerization of the compound represented by the general formula [I], a usual vinyl polymerization method can be applied, and a polymer is appropriately obtained by a radical polymerization method or an ionic polymerization method according to the reactivity of the double bond. In the case of the radical polymerization method, it is preferable to perform polymerization at a temperature of −50 ° C. to 100 ° C. using a peroxide, an azo compound or the like as an initiator.In the case of the ionic polymerization method, an initiator such as an acid or a base is used. Preferably, the polymerization is carried out at a temperature of -100C to 100C. Also,
Using various sensitizers, a polymer can be obtained by a photopolymerization method or a radiation polymerization method. As the polymerization process, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be appropriately adopted.

According to the polymerization method described above, a homopolymer of the compound represented by the general formula [I], a polymer of two or more compounds selected from the compounds represented by the general formula [I], a compound represented by the general formula [I] and Any of the copolymers with the above monomer can be produced, and examples of the obtained copolymer include a random copolymer and a block copolymer.

Monomers copolymerizable with the compound represented by the general formula [I] include olefins such as ethylene, propylene and butylene; acrylic acid and its salts; acrylic esters such as methyl acrylate and butyl acrylate; methacrylic acid and Methacrylates such as methyl methacrylate and butyl methacrylate; vinyl esters such as vinyl acetate; vinyl ethers such as methyl vinyl ether; acrylonitrile; methacrylonitrile; acrylamide, methacrylamide and derivatives thereof; And conjugated dienes such as butadiene and isoprene. The unit content corresponding to the compound represented by the general formula [I] in the copolymer obtained by copolymerization with these copolymerizable monomers varies depending on the purpose of use of the copolymer.
It is preferably at least 10 mol%, and more preferably at least 10 mol%, and at such a content, a function specific to a polymer containing a porphyrin ring in the side chain is exhibited.

The molecular weight of the homopolymer or copolymer obtained using the porphyrin compound represented by the general formula (I) is 3,000
The molecular weight is more preferably 5,000 or more and 10,000,000 or less, and particularly when a film or the like is formed, a polymer having a high degree of polymerization is preferable.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 (a) Synthesis of 2-hydroxymethyl-5,10,15,20-tetraphenylporphyrin copper (II) (hereinafter abbreviated as HOMTPPCu) Momentean et al. (Momentean et al.), Canadian・ Journal of Chemistry (Can.J.Che
m.), 57 1804 (1979).
After adding 2 l of chloroform to 3.02 g of formyl-5,10,15,20-tetraphenylporphyrin copper (II) (hereinafter abbreviated as FTPPCu) and stirring at room temperature for 30 minutes or more, 24.0 g of sodium borohydride Is heated and dissolved in 700 ml of ethanol.
The mixture was dropped and stirred over 30 minutes. During the addition, the color of the solution changed from deep purple to bright red. After stirring for another 40 minutes,
It was washed five times with 800 ml of water and dehydrated with anhydrous magnesium sulfate overnight. After removing magnesium sulfate, the solvent was distilled off,
After drying at 120 ° C. for 10 hours, 2.88 g of a purple powder was obtained. 95% yield
It was. The powder to be HOMTPPCu is ^[nu OH to 3580cm ^-1 was observed in the infrared absorption spectrum, ^ν C = 0 of 1658 cm ^-1 observed in FTPPCu was confirmed from the fact and elemental analysis are missing.

(B) 2-acryloyloxymethyl-5,10,15,20-
Tetraphenylporphyrin copper (II) (hereinafter AOMTPPCu
Synthesis of [Compound No. 35] Chloroform 1 and triethylamine (75.0 ml) were added to HOMTPPCu (3.04 g), and the mixture was stirred in an ice bath for 30 minutes.
Minutes. The solution was concentrated to about 200 ml, and methanol 1 was slowly added. The resulting precipitate was filtered, washed several times with methanol, and dried at 80 ° C. under reduced pressure. Subsequently, 600 ml of benzene was added, the mixture was heated under reflux for several hours, filtered to remove impurities, and subjected to column chromatography on silica gel to collect a first component. Remove the solvent and remove under reduced pressure.
Drying at 0 ° C. gave 2.12 g of a red-purple powder. The yield was 64.8%. Is that this powder is AOMTPPCu, infrared absorption spectrum (measured by KBr tablet method), ν ^C = 0 to 1720 cm ^-1
Was observed, and the disappearance of 3580 cm ^{−1 ν} OH observed by FTPPCu was confirmed by elemental analysis. FIG. 1 shows the infrared absorption spectrum, and the elemental analysis values are shown below.

Elemental analysis Calculated value C: 75.82%, H: 4.24%, N: 7.37% Actual value C: 76.02%, H: 4.40%, N: 7.15% Example 2 (a) Hydroxymethyl-5,10,15, Synthesis of 20-tetraphenylporphyrin vanadyl (II) (hereinafter abbreviated as HOMTPPVO) 2-Formyl-5,10,15,20-tetraf synthesized according to the method described in the literature by Moentian et al. Enilporphyrin vanadyl (II) (hereinafter abbreviated as FTPPVO)
After adding 1.4 l of chloroform to 2.04 g and stirring and dissolving at room temperature, a solution prepared by heating and dissolving 13.1 g of sodium borohydride in 470 ml of ethanol was added dropwise with stirring for 15 minutes. During this time, the color of the solution changed from deep purple to bright red. After continuing stirring for 40 minutes, wash with water 5 times with 800 ml of distilled water.
Anhydrous magnesium sulfate was added and dehydrated overnight. After removing magnesium sulfate, the solvent was distilled off, and dried at 100 ° C. under reduced pressure to obtain 1.93 g of purple powder. The yield was 96%. The fact that this powder is HOMTPPVO is 3580 cm in the infrared absorption spectrum.
^{-1 ν} OH was observed, and 1658 cm ^{-1 ν} observed by FTPPCu
It was confirmed from disappearance of C = 0 and from elemental analysis.

(B) 2-acryloyloxymethyl-5,10,15,20-
Tetraphenylporphyrin vanadyl (II) (hereinafter AO
Synthesis of [Compound No. 37] To 2.01 g of HOMTPPVO, 740 ml of chloroform and 90 ml of triethylamine were added, and the mixture was stirred for 30 minutes in an ice bath. Then, the acrylic acid chloride was added dropwise over 30 minutes while stirring, and further stirred for 60 minutes. did. Then, the mixture was washed 10 times with 1N hydrochloric acid (500 ml), the solvent was distilled off as much as possible, methanol was added to form a solution, and the same volume of water as methanol was slowly added with stirring to obtain a precipitate. After filtering the resulting precipitate, water-methanol (volume ratio 1 /
Washed several times in 1) and dried at 100 ° C under reduced pressure. Subsequently, the resultant was heated and dissolved in 500 ml of benzene, and subjected to column chromatography on silica gel to collect a first component. The solvent was distilled off as much as possible, dissolved in methanol, and then water was added slowly and left overnight. Filter the resulting precipitate and remove
Drying at ℃ yielded 1.30 g of red-purple powder. The yield was 60%. That the powder is AOMTPPVO is, ^[nu C = 0 to 1740 cm ^-1 in the infrared absorption spectrum (measured by KBr tablet method) is observed, ^{the [nu} OH of 3580cm ^-1, which is observed in FTPPVO is lost And elemental analysis. FIG. 2 shows the infrared absorption spectrum, and the elemental analysis values are shown below.

Elemental analysis Calculated value C: 75.49%, H: 4.22%, N: 7.34% Analysis value C: 75.81%, H: 4.38%, N: 7.12% Examples 3-7 Various polymerizabilities as in Example 1 A porphyrin compound was synthesized. Table 2 shows reaction raw materials, reaction conditions (solvent / catalyst / reaction temperature / reaction time) products and their yields.

^{(Note) P 1, P 2, P} 3 in Table 2, P ⁴ and P ⁵
Means the same as P ¹ , P ² , P ³ , P ⁴ and P ^{5 in} Table ¹ , respectively.

Reference Example 1 0.7 g of AOMTPPCu [Compound No. 35] obtained in Example 1 was placed in a reaction tube, and 2,2′-azobisisobutyronitrile (prepared to a concentration of 5.21 × 10 ⁻³ mol / l in advance) Below, AIB
1.90 ml of a benzonitrile solution (abbreviated as N) was added, and the mixture was frozen and degassed three times by a conventional method, and then sealed. It was set on a shaker and polymerized at 60 ° C. for 50 hours with shaking. After the completion, the reaction tube was opened, diluted with benzene, and then poured into acetone to precipitate a polymer. Subsequently, the reprecipitation operation was repeated four times using benzene as a solvent and acetone as a precipitant, purified, and dried at 40 ° C. under reduced pressure. The polymer yield was 0.07 g and the polymerization yield was 10%.

The infrared absorption spectra of both the obtained polymer and AOMTPPCu were measured by KBr method and the two were compared.
The absorption of the porphyrin ring present in ^-1 hardly differs between the two, and it was confirmed that the obtained polymer was a polymer obtained by polymerizing AOMTPPCu with a vinyl group [hereinafter abbreviated as poly (AOMTPPCu)]. Was. Next, GPC was measured at 40 ° C. using THF as a solvent. As a result, w = 1.16 × 10 ⁴ and w / n = 1.78. (W: weight average molecular weight, n: number average molecular weight) Also, the visible absorption spectrum was measured with a benzene solution,
Compared with AOMTPPCu, poly (AOMTPPCu) showed hypochromism and broadening in the absorption of the Sole band near 420 nm, suggesting that poly (AOMTPPCu) has an interaction between porphyrin rings. . In addition, absorption characteristic of poly (AOMTPPCu) was observed around 630 nm.

Reference Example 2 0.50 g of AOMTPPVO [Compound No. 37] obtained in Example and A
Take 0.50 g of OMTPPCu (Compound No. 35) into a reaction tube, and add 4.75 ×
2.0 ml of a benzonitrile solution of AIBN previously adjusted to a concentration of 10 ⁻³ mol / l was added, and the mixture was subjected to a freeze degassing operation three times by a conventional method and then sealed. It was set on a shaker and polymerized at 60 ° C. for 50 hours with shaking. After the completion, the reaction tube was opened, diluted with benzene, and then poured into acetone to precipitate a polymer. Subsequently, re-precipitation was repeated four times using benzene as a solvent and acetone as a precipitant, followed by purification.
Dried at 40 ° C. The polymer yield is 0.1g and the polymerization yield is 10%
It was.

According to the infrared absorption spectrum measurement by the KBr method, 600 to 90
The portion due to the porphyrin ring absorption at 0 cm ^-1 is almost the same as the monomer, and the obtained polymer is AOMTPPVO and AOMTPPCu.
Is a copolymer obtained by copolymerization with a vinyl group [hereinafter referred to as poly (AO
MTPPVO-Co-Cu)].
Next, GPC was measured at 40 ° C. using THF as a solvent.
= 7,700, w / n = 1.2. The visible absorption spectrum was measured with a benzene solution.
Hypochromism and broadening were observed in the sole absorption band near m, indicating that poly (AOMTPPVO-Co-
It was suggested that Cu) has an interaction between porphyrin rings. In addition, absorption peculiar to the polymer was observed around 630 nm.

(Effect of the Invention) According to the present invention, a novel porphyrin compound represented by the aforementioned general formula [I] is provided. The compound provided by the present invention can be easily produced, and can be easily homopolymerized or copolymerized with another porphyrin compound represented by the general formula [I] or another type of copolymerizable monomer to obtain a polymer. (Among others, linear polymers). Interaction between the porphyrin rings is observed in the obtained polymer, and such a polymer is useful as an oxygen carrier material, a recording material, a photochemical hole burning material, and a magnetic material. Further, a polymer containing a large amount of structural units based on the compound represented by the general formula [I] has high heat resistance, and therefore, applications utilizing this point are also expected.

[Brief description of the drawings]

FIG. 1 shows the 2-acryloyloxymethyl-5,10,15,20-tetraphenylporphyrin copper (I) obtained in Example 1.
FIG. 2 shows an infrared absorption spectrum of I). FIG. 2 shows 2-acryloyloxymethyl-5,1 obtained in Example 2.
0,15,20-tetraphenylporphyrin vanadyl (II)
FIG. 3 is a diagram showing an infrared absorption spectrum of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 20/34 C08F 20/34 20/38 20/38 20/60 20/60 26/02 26/02 28/00 28/00 28/04 28/04 // C09B 47/00 C09B 47/00

Claims (1)

(57) [Claims] (1) General formula [Wherein, R ^a , R ^b and R ^c each represent a hydrogen atom or a lower alkyl group; (R ^d represents a lower alkyl group), ( ^Re represents a hydrogen atom or a lower alkyl group) and represents one group selected from the group consisting of: Y represents an alkylidene group having 1 to 5 carbon atoms, or -O-, (R ^f represents a hydrogen atom or a lower alkyl group), (R ^g represents a hydrogen atom or a lower alkyl group).
And Z represents -O- or And r represents 0 or 1, when r is 0, s represents 0 or 1, and t represents 1, when r is 1, s represents 1, and t represents 0 or 1. And P is (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
^10, one of among R ¹¹ and R ¹² are defined or below represents a bond ^{R 1, R 2, R 3} , R 4, R 5, R 6, R
^{7, R 8, R 9,} R 10, R 11 or one of radicals represented by R ¹²
R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a phenyl group which may have a lower alkyl group or a hydroxyl group as a substituent, or a lower alkyl group as a substituent. Represents a pyridyl group which may have R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may each have a hydrogen atom or a hydroxyl or lower alkoxycarbonyl group as a substituent. Represents a certain lower alkyl group, and M represents a metal).