JPS62129270A - Novel bipyridine derivative - Google Patents

Abstract

NEW MATERIAL:4,4'-Bis(hydroxymethyl)-2,2'-bipyridine shown by formula I. USE:A photosensitizer using solar energy. PREPARATION:4,4'-Dimethyl-2,2'-bipyridine shown by formula II is oxidized with KMnO4 in water to give a 4,4'-dicarboxy derivative, which is chlorinated with SOCl2 under reflux for 3-4hr, successively esterified with CH3OH under reflux for 2-4hr to give a 4,4'-bis(methoxycarbonyl) derivative, which is reduced with NaBH4, etc., to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel bipyridine derivative useful as a photosensitizer for utilizing solar energy.

[Background of the invention]

Today, energy issues are rapidly gaining importance, and as many new and alternative energies are being explored, expectations for the use of solar energy are also increasing. Sunlight is naturally converted into various forms of energy. As a method for artificially converting solar energy, which is characterized by being dilute and proportional to area, there are three types of conversion methods: converting it into thermal energy, electrical energy, or chemical energy. For thermal conversion, solar heating and cooling systems are becoming more and more practical, and for electrical conversion, ultra-thin amorphous silicon solar cells are becoming more practical. Conversion into chemical energy is based on chemical processes that involve changes in matter, and active research activities are currently underway.

Conversion and storage of solar energy based on chemical processes include photosynthesis, high energy substances (high strain compounds)
, photochemical cells, photocatalytic reactions, etc. are currently being researched.

The production of high-energy substances by artificial photosynthesis systems based on photosynthetic simulation, such as the production of hydrogen by water decomposition, is an extremely important research goal from the perspective of solar energy utilization. For example, even if we use the well-known reversible photoisomerization of nordernasienes and quadricyclenes, the amount of stored heat is as small as 1.2 kJ/11, but when hydrogen is obtained by artificial photosynthesis, its combustion fever is 140
It reaches as much as kJ/l. In this way, we can isolate the main components in photosynthesis such as hematoporphyrin, tetraphenylporphyrin manganese complexes, bipyridine manganese complexes, chlorophyll and chloroplasts, or the photochemical effects of n-type semiconductor TiO7 and ruthenium ( ■
) Attempts are being made to photolyze water by utilizing the catalytic action of metal complexes such as trisbipyridine complex (Ru(bpy)3).

Among these; Ru(bpy)3 exhibits an absorption spectrum that broadly overlaps with the wavelength distribution of sunlight, and generates an excited state *Ru(bpy)3 with good yield when irradiated with visible light, but its lifetime is relatively long. In addition, due to its strong reducing power, its use as a photosensitizer in the use of solar energy has been widely attempted. From this point of view, there is a report that the substituent R of the trisbipyridine complex of ruthenium shown by the following formula is a long chain fatty acid, and it is arranged as a monomolecular film on a glass plate and water is decomposed by visible light irradiation. is said to have been unsuccessful. In addition, although research on artificial photosynthesis seems to have overcome the fundamental hurdles, there are still issues to be solved, such as how to adapt the effective wavelength range to the solar spectrum, how to increase the quantum yield, and how to obtain materials that can be used for long periods of time. There are many challenges that need to be overcome.

[Purpose of the invention]

The present invention relates to the production of hydrogen by photolysis of water.
It also concerns how to effectively utilize the solar energy proportional to the area.The effective wavelength range matches the solar spectrum, the quantum yield is high, it can be used for a long time, and the photolysis of water can generate light energy. The purpose of the present invention is to provide a new bilysine derivative that can efficiently convert into chemical energy.

[Structure of the invention]

The present invention provides 4,4'-bis(hydroxymethyl)-2,
This is an invention of 2'-bipyridine.

The synthetic route for the compound of the present invention is as follows.

That is, for example, J, Am, Chem, Sac, +
9'14947 ('1977), 4,4'-dimethyl-2,2'-bipyridine is oxidized with KMnO4 in H20 to form 4,4'-dicardexy2.
Since 2'-bipyridine is obtained, it is chlorinated with 5OC22 (refluxing for 3 to 4 hours) according to the same literature, and then chlorinated with C
Esterification with H6OH (refluxing 2-4 hours) gives 4.
The yield from 4'-dicarboxy-2,2'-bipyridine was about 70%, and 4.4'-bis(methoxycarbonyl) -
2,2'-bipyridine is obtained. By reducing this with a suitable reducing agent, the desired 4,4'-bis(hydroxymethyl)-2,2'-bipyridine can be obtained. Suitable reducing agents include inorganic and organic metal hydride compounds such as NaBHa (sodium borohydride) and RDB (sodium dihydrobis(2-methoxyethoxy)aluminate). LiAtHa has too strong a reducing power, and it is difficult to selectively proceed with the desired reduction reaction.

Reference examples and examples are shown below.

〔Example〕

Reference example 4,4'-bis(methoxycarbonyl)-2,
Synthesis of 2'-bipyridine (1) Synthesis of 4'-dicardexy-2,2'-bipyridine 4.4'-dimethyl-2,2'-bipyridine 96F and potassium permanganate 300! A reflux reaction was carried out in i'e water 31 for 12 hours. After the reaction, the brown precipitate was removed in an oven, and the resulting yellow solution was washed with ether to remove unreacted raw materials. Concentrated hydrochloric acid was added to precipitate crystals, which were then washed with water and dried for 4 hours.
．． White crystals of 4'-dicardexy-2,2'-bipyridine 55.2F (yield: 57%) were obtained.

(2) 4.4'-bis(methoxycarbonyl) -2,
4,4'-dicardexy 2,2'-bipyridine obtained in synthesis (1) of 2'-bipyridine48. :ll and 2400rrLl of 5OCL were mixed, heated under reflux for 4 hours, the reaction solution was concentrated, 60 Qlnl of toluene and CH30H22mj were added thereto, and heated and refluxed for an additional 2.5 hours. After the reaction,
After extraction with chloroform, the organic layer was separated, washed with an aqueous NaHCO5 solution and then with water, and then dehydrated and dried over anhydrous Na2SO4. After the dehydrating agent was removed, the solvent was distilled off and the residue was recrystallized from acetone-chloroform to give 4,4'-
Bis(methoxycarbonyl)-2,2'-bipyridine (38.51% yield, 70.7%) was obtained. mp208-21
0℃.

Elemental analysis value (C44H42N2o4) Theoretical value: C, 61,76: H, 4,44S N,
10.29 Actual value: C, 61,58: H, 4,39:
N, 10.4ONMR (inCDC23) δ11m: 4.01 (6H,9, (CH,-)N2)7.90
(2H, d, J = 5Hz, pyridine ring 5th position,
H at position 5') 8.88 (2H, d, J = 5Hz, 6th position of pyridine ring, H at position δ6) 8.97 (2H, broads + 3rd position of pyridine ring,
H at the 3' position) Example 1 4,4'-bis(methoxycarbonyl)- obtained in Reference Example
15.7 g of 2,2'-bipyridine was added to 300 g of ethanol.
The mixture was reacted with NaBH412.7ji in m1 under heating under reflux for 2 hours.

After the reaction, the reaction solution was concentrated, water and ethyl acetate were poured in, and after stirring, the organic layer was separated, washed with water, and then diluted with anhydrous Na2S.
It was dehydrated and dried with O4. After removing the dehydrating agent, the solvent was distilled off, and the crystallized residue was recrystallized from ethyl acetate to give 5.0# of 4,4'-bis(hydroxymethyl)-2,2'-bipyridine (harvested) as white needle-like crystals. rate 41.3) was obtained. mp17
2.5-174°C.

Elemental analysis value (C42H1□N202) Theoretical value: C, 66, 65: H, 5, 59: N, 12
．． 95 actual measurement value: C, 66,49: H, 5,53:
N, 12.92NMR(in DMSO-d, )δ
ppm'4.61~4.70 (4H1m, (-CH
2-) X 2 ) 7.40 (2H, d, J =
5Hz, H at the 5th and 5' positions of the pyridine ring) 8.43 (2H,s, H at the 3rd and 3' positions of the pyridine ring)
GC/MS (Mw216): 216 (M+) IRI'c
rn'''' (KBr): 3320 (OH),
2850(-CH2-), 1585(-C=(=
) Example 2 4,4'-bis(methoxycarbonyl)- obtained in Reference Example
2,2'-bipyridine 1.61 to tetrahydrofuran 1
50mA! To this was added dropwise 16.2.9 i of a toluene solution of sodium dihydrobis(2-methoxyethoxy)aluminate at 0°C under a N2 stream, and the mixture was reacted at room temperature for 1 hour. After the reaction, ammonium chloride aqueous solution is injected,
The liberated oil was extracted with ethyl acetate and treated in the same manner as in Example 1 to obtain 4,4'-bis(hydroxymethyl)-2,2'-bipyridine 0.5 & (yield 38 .5%) was obtained. mp1725-174°C. Elemental analysis values, NMR, GC/MS of this product.

and IR supported that it was 4,4'-bis(hydroxymethyl')-2,2'-bipyridine.

〔Effect of the invention〕

The present invention provides a novel bipyridine derivative useful as a photosensitizer for utilizing solar energy, etc. When the compound of the present invention is used, in the production of hydrogen by photolysis of water,
Solar energy, which is dilute and proportional to area, can be used extremely effectively. That is, the novel bipyridine derivative of the present invention provides a ruthenium complex whose effective wavelength range matches the solar spectrum, has a high quantum yield, can withstand long-term use, and efficiently converts light energy into chemical energy through photolysis of water. obtain. The compound of the present invention also has an active hydroxyl group (-CH
2-0) Ri'! ), it can be easily combined with water-soluble or oil-soluble polymers through ester bonds, etc., or can be easily combined with glass substrates by silylation, improving catalytic function, expressing hybrid function, etc. It is highly expected that various functions will be improved and new functions will be developed.

Patent Applicant: Wako Pure Chemical Industries, Ltd. Procedural Amendment Form February 24, 1988 1985 Patent Application No. 270550 2, Title of Invention: New Bipyridine Derivative 3, Relationship with the person making the amendment Patent Applicant: 541 Address: 3-10, Doho-cho, Higashi-ku, Osaka-shi, Osaka Prefecture Contact information: Patent Law (Tokyo) 03-270-85715, detailed description of the invention in the specification to be amended.

6. Contents of amendment (1) "Theoretical value:" written on page 8, line 15 of the specification is amended to "Theoretical value (X): J."

(2) "Actual value:" written on page 8, line 16 of the specification is corrected to "Actual value ($): J."

(3) "Theoretical value:" written on page 9, line 16 of the specification is corrected to "theoretical value (χ):".

(4) "Actual value:" written on page 9, line 17 of the specification is corrected to "Actual value ($): J," (5) "Many" written on page 11, line 16 of the specification. to be corrected to "a great deal."

that's all

Claims (1)

[Claims] 4,4'-bis(hydroxymethyl)-2, represented by the formula, ▲Mathematical formula, chemical formula, table, etc.▼
2'-Bipyridine.