JPS5920261A - Method for promoting atomic valence isomerization - Google Patents

Abstract

PURPOSE:To carry out the atomic valence isomerization of a quadricyclane-type highly strained organic compound to a norbornadiene organic compound useful as a photochemical solar energy storage substance, in high efficiency, by using a specific catalyst. CONSTITUTION:The quadricyclane of formula I , or a quadricyclane compound wherein at least one of the H atoms of 2, 3, 5 and 6-positions is substituted, is converted to a norbornadiene of formula II or a norbornadiene compound wherein at least one of the H atoms of 2, 3, 5 and 6-positions is substituted, by contacting the quadricyclane compound with a catalyst comprising a metal complex of a water-soluble nitrogen-containing polycyclic compound having one or more hydrophilic groups on the porphyrin skeleton or the phthalocyanine skeleton, in an aqueous solution at normal temperature and pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for promoting valence isomerism in a valence isomer compound known as a photochemical solar energy storage material, and specifically to a method for efficiently converting a quadriquinone-based highly strained organic compound into norbornadiene. This invention relates to a method for valence isomerization of organic compounds.

Photochemical solar energy storage systems using highly strained organic compounds have been attracting attention in recent years, but the most promising of these are the highly strained organic compounds of Quadrisaicone [hereinafter referred to as QC compounds (1)] and norbornagen. system organic compound [hereinafter referred to as ND compound (())], the valences of madder (I) (II) shown by the following formulas [However, QC compound (I) and ND compound (2°8, 5. The hydrogen atom at position 6 may be substituted with any substituent, the same applies hereafter] In other words, when ND compound (II) is irradiated with sunlight, valence isomerism occurs and becomes QC compound CI) υ, and conversely Under heat or a catalyst, it returns to the ND compound (]II, where (I
Solar energy is absorbed and stored through the I)-(I) conversion, and the energy is dissipated through the (I)-(II) conversion. Therefore, in order for this system to efficiently utilize solar energy, it is necessary to use compound (II) such that the (II)-(,I) reaction by solar energy can easily proceed, and from compound (I) to Two points are extremely important: allowing the return v reaction to compound (II) to proceed efficiently and without any hindrance. Regarding the former point, QC compound (I) and ND
Knowing that a great improvement could be obtained by changing the types of substituents at the 2°8 and 5.6 positions of compound (II), he had already filed a patent application (Japanese Patent Application No. 1986-21).
No. 4186). In the present invention, the latter point, that is, the conversion reaction from the QC compound (I) to the ND compound (I[) is to proceed efficiently by selecting an appropriate catalyst.
The main focus was on various studies, both compounds (I),
We have completed a method that allows the above conversion reaction to be carried out with high efficiency regardless of the substituents at the 2, B, and 5.6 positions in (II).

That is, the present invention deals with the conversion of the QC compound CI) to the ND compound (1) using a compound having one or more hydrophilic groups on the porphyrin skeleton or phthalocyanine skeleton, that is, a metal of a water-soluble nitrogen-containing polycyclic compound. The key point is that a complex is used as a catalyst. In the above catalyst, the compound having a porphyrin skeleton has the general formula () (where R1, R", R", R', R', R', R7,
R', R9, R10゜Rll and R12 are the same or different and are hydrogen or any substituent, provided that R1
- At least one of R12 must be a hydrophilic group) A water-soluble nitrogen-containing polycyclic compound is used, and a compound having a phthalonanine skeleton has at least 1111 hydrophilic groups in the benzene nucleus, Water-soluble nitrogen-containing polycyclic compounds which may have other optional substituents are used, and these are all Fe, Co, N
l, Cu, Zn, Pd.

It is applied to the present invention as a complex with a metal selected from Rh. Examples of the hydrophilic groups substituted in the above porphyrin skeleton and phthalocyanine skeleton include carboxy μ groups and sulfone groups, and cholera is exemplified when each hydrogen of the indole nucleus, benzene nucleus, and methine group is directly substituted. Without limitation, alkyl/L' groups (e.g. methyl,
Lower alkyl/L/) such as ethyl, propyl, butyl, alkenyl group (lower 7μ such as vinyl, aryl, etc.)
Allyl groups (for example, lower acyl such as acetyl and propionyl), etc. may be fully substituted. Groups (specifically non-hydrophilic groups) that can be substituted with other than the above-mentioned hydrophilic groups include 7/L'kyl group (same as hydration), alkenyl group (same as hydration), allyl group (same as hydration) , formyl, halogen, allyl group (phenyl, etc.)
, alkylthio (e.g., lower alkylthio such as methylthio, ethylthio, propylthio, etc.), alkoxy (e.g., methoxy, ethoxy, propoxy, lower alkoxy of methane), and these groups further include hydroxy groups, mercapto groups, halogens, and alkoxy groups. V&, alkylthio group, acyl group, 7μ koxycarbonyl group, small lumyl group, primary and secondary are also 1. < may be substituted with an 8th-class amine 7 group, etc. Therefore, porphyrin-type compounds (DI) and phthalocyanine-type compounds (IV)'k having such substituents and satisfying the conditions of the present invention, more specific examples include glotoporphyrin and deutroporphyrin. , hematoporphyrin, mesoporphyrin,
Diacetyl deutroporphyrin, diformyl deutroporphyrin, nupirographisporphyrin, isospirographisporphyrin, porphyrin C.

heme a1 porphyrin a1 urophorphyrin, cobrovorphyrin, peptoborphyrin, porphyrin S-
411, haderophorphyrin, phytolochlorin e,
Hematoporphyrin, hematin, chlorophyll a, same, phylloerythrin, deoxyphylloerinulin, pheophorbite a, same, phaeophytis, same b
Examples include 1-phthalocyanine tetonurphonic acid.

If such a porphyrin-type compound (DI3 and a phthalocyanine compound) is used alone or in combination of two or more to act on the QC compound (I), it is very easy to use the ND compound (
1). The reaction conditions in this case may be extremely mild, and the QC compound (I) and the catalyst ([
It is sufficient to contact 1) or (N)' in an aqueous solution under normal pressure, and the reaction proceeds kinetically in a condensed manner. When preparing an aqueous solution of (II'[) or (]V), use carbonic acid) Urum, potassium carbonate, sodium hydrogen carbonate, potassium hypoacid aqueous solution, sodium hydroxide,
Prepare an aqueous solution such as potassium hydroxide, add the catalyst (11
) or (■), and compared to conventional techniques that use heavy metal catalysts such as Ag and PT, this method is much superior in terms of operability and waste liquid treatment stoppage. can.

The QC compound (I) to which the method of the present invention is applied is not particularly limited, but compounds represented by the following general formula are particularly preferred [wherein R18 and R
are the same or different, -CONH-(aryl
'), -CONH-a, l'kil, -CONH
-(arene)-alkoxy.

ldR"l: R15 is carboxy or alkoxyl (lv), or R1B and R14 jointly (
aryl) -co-A-6゜-] In addition, to explain the meaning of each substituent in the above general formula (■), aryl in R and R14 refers to phenyl, 1-naphthyl, , 2-naphthyl/醇'e りみし 1rukyl means t-butyl and the like. In addition, keruarene refers to all of 0-phenylene, m-phenylene, and p-phenylene, and the alkoxy carbonyl represented by IJuKRl 5 includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and isopropoquine carbonyl. .

butoxycarbonyl, 8th-class butoxycarbonyl)v.

Bentyloxycarbonyl, hexyloxycarbonyl/
All examples of lower alkoxycarbonyl/I/ such as I/ can be given.

Although there are no particular restrictions on the method of producing these compounds, a typical production route is as follows. However, these compounds are produced as compounds having a norbornadiene skeleton, and are made to have a valence to the quadrizycran skeleton by irradiating them with sunlight. Examples of the alkyl μ include lower alkyl/L”i such as methyl, ethyl, propyl, isopropyl 8th-butyl, pentyl, and t\xy/L/.

The chemical reactions utilized in the example manufacturing procedure above include dehydration,
These include amidation reactions, imidization reactions, esterification reactions, etc., and there are no restrictions on the reaction conditions, but in all cases, it is recommended to carry out the reaction by cooling or heating in the presence of a solvent. .

Next, an embodiment of the present invention will be described.

Example 1 8-phenylcarbamoyl quadrizycran-2-carciboxylic acid lO. When the cobalt complex salt of hematoporphyrin was added to an aqueous solution (0.21 mm/I/) of sodium suboxide of 5 da (0.041 mm/I/), the reaction proceeded rapidly at room temperature, and the 8-phenyl force Lupamoinorbornadiene-2-carboxylic acid (10,5) was obtained.

ml) 151~152'O (dec)IR(K
Br) 8000~8600z (br, CO2
H).

1-1 8800tM (NH), 169(X+ (C=0)
'H-NMR (CD0g8) J 2,08 ~2.50 (m, 2H), 4.25 (m.2
H1, 6.98 (m, 2H), 7.2 ~ 7.8 (m,
5H), 9.17 (br.

LH), 12.6 to 18.7 (br, LH) Similarly, the following norbornadiene compounds were obtained from the corresponding quadricyclohexane compounds.

8-(1-Naphthyl Rubamoy/I/) norbornadiene-2-carboxylic acid mp (acetone-ether recrystallization) 184 ~1
87"0 (dec) IR (KBr') 8800~
2600on (br.cO□HINH)1 167(lc* (C=0) 11(-NMR (CDCI 8) al, 96~2
．． 80 (m, 2H), 4.1Bm, IH), 4.22 (
m, IH), 6.88 (m.2H), 7.8-8.0 (
m, 7H).

9, 77 (br, LH), 10.4 ~ 11.5 (br
, IH) 8~(p-methoxyphenylcarbamoy/L/
) norbornadiene-2-carboxylic acid mp 179-180°C 11 R (KB r) 2800-8400 (b
r, CO2)1).

1-1 8260c1s (NH), 1675ff (C=0
).

1600rM-''H-NMR (CDCN 8) J2, 1 ~ 2
．． 4 (m, 21 (), 8.82 ([i, 8) 1), 4.
08 (m.

211), 6.8 to 7.0 (m, 2B), 6.96 (
m, 2H'), 7.4-7.6 (m, 2H), 8.44
(br, LH), 10.7(br.

IH) N-phenylnorbornadiene-2,8-dicarboximide mp (benzene-petroleum ether recrystallization) 119-121
°C (dec) IR (KBr) 1760cm (C=O), 1
705ff'(C=03' H-NMR (CDCe
8) J2, 62 (m, 2H), 4.02 (m, 2H
), 6.90 (m.

2H), 7.2 to 7.6 (m, 5H
)N-(1-naphthi/I/)norbornadien-2,8
-dicarboximide mp (benzene-petroleum ether recrystallization) 1 8 0
~l 8 2”0 (dec)IR(KBr)
1760m-' (C=0), 1700z (C=O)
'H-NMR (CDCe 8) δ 2.66 (m, 2H), 4.07 (m, 2H), 7.0
0 (m.

2H), 7.2-8.0 (m, 7H) 8-phenylcarbamoylnorbornadiene-2-methylcarboxylate) (oil) 1-1 1R (NaC4?) 8250o++ (NH)
, 1685C+++ (C=O).

1 1660α (C=0)' H-NMR (CDCe 8'I al, 96-2.
26 (m, 2H), 8.85 (a, 8H).

4.10 (m, LH), 4.86 (m, IH), 6.9
0 (m.

2H), 7.0-7.4 (m, 811), 7.
6-7.8 (m, 2H) norbornadien-2,8-
Dicarboxyanilide mI) 195-196.5℃ 1-1 1R (KBrl 8280an (br,
NH)+1650(''(C=03'H-NMR (CDC68) δ 2.0-2.8 (m, 2H), 4.18 (m, 2H).

6.96 (m, 2H), 7.0-7.4 (m, 8H).

7.5-7.7 (m, 2H), 9.86 (br, 2H)
8-phenylcarbamoylnorbornadiene-2-carboxylic acid ml) (CH2Ce2-ether recrystallization) 151-15
2°0 (dsc) 1 1 R (KB r) 8000~8600 pieces (br
, C02H).

1-1 88007m (NH), 690C7+1 (C=
0')' II-NMR (CDCe 8) J2.08
~2.50 (m, 2H), 4.25 (m, 2H).

6.98 (m, 2H'), 7.2-7.8 (m, 5H)
, 9.17 (br, LH), 12.6-18.7 (br
,LH)Uv(2XlO-2M, NaOH aqueous solution"n
1a) ((ε) 8080m (7000) 8-(t-butylcarbamoylene-2-carboxylic acid"I' (CH2Cg2-hexane recrystallization) 200-201°Cl IR (KBr) 8200-8600o++ (
br, COOH/).

8800cm-' (NH), 1680im'
(C=O)1H-NMR (CDCI 8) al,
45 (11, 9H), 2.0 ~ 2.82 (
m, 2H1, 8.7 ~ 8, 9 (m, IH), 4
．． 1 ~ 4.25 (m, 1B), 6.2 ~ 6, 5 ~
(br.IH), 6.85 ~ 7.02 (m.2H)t
lVC2 0-2M NaOH aqueous solution) 29O
r1m (lih) compound mp (diluted hydrochloric acid reprecipitation stage) 800°0 or more I R
[KBr) 8100~8700cm
(br, CO2H) +16800II (
C=O)'H-NMR (NaHCO2-D20) δ2,8
~2.6 (4H, m), 4.8 ~4.5 (4B, m
).

7, 8-7.4 (4H, m), 7.85 (4H, a) U
V ('NaHC08 aqueous solution) λmaX (ε) 887, 5
1m (12400) 287nm Compound mP (re-precipitated with HCI aqueous solution) 800°C or higher IR
(KBr) 8200~8700Ca (br,
CO2H).

1 8270α (NH/), 1690 mouths (C=O
) 'H-NMR (NaHCO8-D20) δ2,8 ~2
．． 7 (m.4H), 8.85CB, 4H), 4.2-4
．． 4 (m, 41), 7.8 ~ 7.5 (m. 41t) U
V (NaHCO8 aqueous solution) λmax (ε) 290 nm (
ah), 2B4.5Bm (10000) Applicant Kazuhiro Maruyama Nato Research Institute Co., Ltd.

Claims (1)

[Claims] (1) A quadricycle compound represented by the formula or a compound in which at least one of the hydrogen atoms at the 2, 8, 5, or 6 position is substituted with an arbitrary substituent is subjected to valence isomerization and is When converting to norbornadiene or a norbornadiene compound in which at least one hydrogen atom at the 2.8.5.6 position is substituted with an arbitrary substituent, one or more on the porphyrin skeleton or haphthalocyanine skeleton A method for promoting valence isomerism, characterized in that a metal lead body of a water-soluble nitrogen-containing polycyclic compound having a hydrophilic group is used as a catalyst.