JPH02865A - Photosensitive material and pattern forming method by using said material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material having good reactivity with an excimer laser of 248.4nm by incorporating a specific photosensitive compd. into said material. CONSTITUTION:The compd. expressed by the formula I is incorporated into the photosensitive material. In the formula I, X denotes a hydrogen atom, -SO3R<1> (where R<1> denotes an alkyl group), etc.; R denotes an alkyl group; cycloalkyl group, etc.; m denotes a natural number. Such compd. has the high reactivity with 248.4nm light and the resist formed by using this compd. has a large change in transmittance before and after exposing and is further increased in the transmittance after exposing. The resin pattern having good shapes is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (F1' Field of Application) The present invention relates to a pattern forming method using a photosensitive material for photolithography and a warp, which is mainly used in the manufacture of semiconductor devices.

(Background of the Invention) In recent years, with the high density and large integration of semiconductor devices, the wavelength used by exposure equipment used for microfabrication, particularly photolithography, has become increasingly shorter, and now rF excimer lasers (248.4 nm) are used. It is now being considered. However, there has not yet been a photosensitive material suitable for this wavelength.

Even when using MP2400 (manufactured by Sibley), which is a currently widely known resist that is said to have fairly high photosensitivity to HrF excimer laser and good light transmittance, the pattern shape after development is very poor. It's so bad that I don't think it will be usable.

For example, the case where a pattern is formed by KrF excimer laser exposure using MP2400 will be explained using FIG. After doing this, a resist 1 and 3 having a thickness of 1.2 .mu.n is obtained (FIG. 4(a)). Next, a 248.4 nm KrF excimer laser 4 is selectively exposed through a mask 5 (see Fig. 4).
b)). Finally, MP2401 (manufactured by Sibley) 2
Resin pattern 3a is obtained by developing for 60 seconds using a 0% aqueous solution (alkaline solution) (Fig. 4(C)).
),.

However, when using MP2400, it is not sensitive to light of this wavelength, so it is necessary to increase the exposure amount, and as a result, light penetrates into the unexposed areas, causing pattern 3a.
As shown in FIG. 4(C), the shape of the structure deteriorated significantly, and an aspect ratio of only about 60 degrees was obtained.

The reason for the poor pattern shape is considered to be that the MP2400 resist has a large surface absorption of exposure light.

This is because the main polymer (resin itself) used in the resist has a large light absorption property against the exposure light, or the photoreactivity of the photosensitive material in the resist is poor. Naphthoquinone diazide photosensitive materials used in resists are generally 248.4r+
For example, MP24, which has a film thickness of 1 mm, has a large absorption of light in the vicinity of u+, and its transmittance does not improve much after exposure.
00, rl' excimer laser (248,4nl)
As shown in FIG. 5, the change in light transmittance of 1-mole wheat exposed using the method was only about 3% at 2411.4 nm, which can be understood to be due to poor reactivity.

Therefore, the emergence of crystalline photosensitive materials that are more reactive to the 248.40 m excimer laser, or in other words, the emergence of photosensitive agents that are more photoreactive to the same laser, is currently being awaited. be.

Photosensitizers developed for this purpose include, for example, a compound having an N20-bonded group reported by Gray (US Pat. No. 4.6).
However, in the compounds specifically disclosed in this patent specification, the functional groups at both ends of the above-mentioned group are simple alkyl groups, aryl groups, or are combined to form an alkylene ring, and when a resist containing these compounds as a photosensitizer is used for photolithography, it is unlikely that the unexposed areas will have a strong blocking ability against alkaline developers. First, it is predicted that the 'Ht resist film will be reduced and the contrast will decrease accordingly, so it cannot necessarily be said that it is a practical photosensitizer.

(Objective of the Invention) An object of the present invention is to provide a pattern forming method using a novel photosensitive material and stiffness that is highly responsive to a 248.4 nm excimer laser.

That is, the present invention has high photosensitivity to deep ultraviolet light around 248.4 nm, and history has involved the development of a photosensitive reagent that has a large change in optical transmittance IA immediately after exposure, and the use of this reagent and light around 248.4 nm. Development of a photosensitive material (resist and contrast enhancement material) that is effective for photophosphorography using light around 248.4 nm in combination with a resin (main polymer) that has a large light transmittance, and the use of this photosensitive material. The purpose of this study is to develop an effective method for forming fine patterns.

[Structure of the invention]

In the present invention, the general formula [I] each independently represents a hydrogen atom or an alkyl group which may have a substituent, or [2, HTh and N combine to form a piperazine ring, a piperidine ring, or a pyrrolidine ring. Alternatively, it may form a ring such as a morpholine ring. ) or react with resin? 1(1) represents an invention of a pattern forming method that includes an alkyl group, a cycloalkyl group, or a hydroxyl group.

Historically, the present invention relates to the general formula [IJ or an alkyl group which may have a substituent,
Alternatively, R5, HG and N may form a ring such as a piperazine ring, a piperazine ring, a pyrrolidine ring or a morpholine ring. ) or a functional group that can react with a resin.

Further, n represents a natural number. ), m represents a natural number.

This invention is a photosensitive material characterized by containing a photosensitive compound represented by ().

Further, the present invention provides a formula [IJ [wherein, X, R and m are the same as above]. After forming a thin film of a photosensitive material containing a photosensitive compound and a resin shown in () on the resist surface of the substrate, it is exposed to deep ultraviolet light, developed, and the layer of the photosensitive material is removed. This invention is a pattern forming method characterized by forming a resist pattern.

Historically, the present invention also relates to the general formula [rl, 1 [wherein, X,
R and m are the same as above. ] R' and R3 are characterized in that a photosensitive material containing a photosensitive compound and a resin represented by the formula is coated on the substrate-F, and then exposed to deep ultraviolet light and developed to form the photosensitive material pattern. Same as ml. Moreover, -5o2cc, -3O2[]r and -5031+ include their quaternary salts. ), H' is an alkyl group, cycloalkyl group, hydroxyalkyl group, alkoxyalkyl group or -(C10.). 6", R4, 115 and R6 are the same as above, and -S l) 2α, -50211r
and -50111 include its quaternary salt. ). Also ,
l represents an integer of 1 to 20), mo represents an integer of 1 to 20. ] This is an invention of a compound represented by.

The compound according to the present invention represented by the formula [IJ includes a functional group. Furthermore, R1 in -5O,R' is, for example, a methyl group, an ethyl group, or a propyl group.

Butyl group, amyl group, hexyl group, heptyl group.

Alkyl groups such as octyl group, nonyl group, decyl group) 3H
4t, such as methyl group, ethyl group, propyl group.

Butyl group, amyl group, xyl group, heptyl group.

Octyl group 1. Examples include alkyl groups such as nonyl groups and decyl groups (which may be linear or branched), or stiff alkyl groups with substituents such as hydroxyl groups and alkoxy groups; Also, R'1. IJ and N may form a ring such as a piperazine ring, piperidine ring, pyrrolidine ring, or morpholine ring. In addition, examples of functional groups that can react with the tree 11n include -802α, -3O2
Br, -5o, H, -COOII.

- may include functional groups such as 0α, -COBr, -Nl12, etc., and -5O2Cl, -5O□Br, -5o3It and -CODll may be quaternary salts thereof,
Examples of bases that can form quaternary salts with these include ammonia, pyridine, piperazine, piperidine, N-methylpyrrolidine, morpholine, diethylamine, and trimethylamine. In the compound according to the present invention represented by the general formula [IJ, R is, for example, a methyl group.

Ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group.

Alkyl groups such as decyl group (which may be linear or branched), e.g. cycloalkyl groups such as cyclopropyl group, cyclobentyl group, cyclohexyl group, e.g. hydroxymethyl group, hydroxyethyl group, Hydroxyalkyl groups such as hydroxypropyl group and hydroxybutyl group, such as methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, and ethoxymethyl group.

Ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, propoxymethyl group, propoxyethyl group, propoxypropyl group, propoxybutyl group, butoxymethyl group, butoxyethyl group.

Or a functional group that can react with a resin can be mentioned. Also, -3
Examples of 1<4 in O3H' include methyl group, ethyl group,
Alkyl groups such as propyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group (whether linear or branched, R5 and R' are hydrogen atoms, e.g. methyl group) , ethyl group, propyl group, butyl group,
Alkyl groups (which may be straight or branched) such as amyl, hexyl, heptyl, octyl, nonyl, decyl, etc., or hydroxyl groups on these alkyl groups.

Examples include those having a substituent such as an alkoxy group, and R5, lli and N may form a ring such as a piperazine ring, piperidine ring, pyrrolidine ring, or morpholine ring. Examples of functional groups that can react with resins include -S02α and -3O2Br.

-3O3H, -GO(Ill, -COα, -COr
, -Nt (2 etc. functional groups are mentioned, -502α, -3
O2Br, -50311 and -(:0011, etc. may be quaternary salts thereof, and examples of bases that can form quaternary salts with them include ammonia, pyridine, piperazine, piperidine, N-methylpyrrolidine. , morpholine, diethylamine, trimethylamine and the like.

In the compound of the present invention represented by the formula [rll, mo is 1
is an integer of ~20, and y is a hydrogen atom -303H (11, R2 and R3 are the same as above), -50
2αdoSO□B” and -3O3H may be quaternary salts, and examples of bases that can form quaternary salts with them include ammonia, pyridine, piperazine, piperidine, N-methylpyrrolidine, and morpholine. , diethylamine, trimethylamine and the like.

2 R7 in the general formula [11] is, for example, an alkyl group (linear (It may be either branched or branched.)
, for example, cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, such as hydroxymethyl group, hydroxyethyl group, hydroxypropyl group,
A hydroxyalkyl group such as a hydroxybutyl group, such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group.

Ethogicibutyl group, propoxymethyl group, propoxyethyl group, propoxypropyl group, propoxybutyl group,
Butoxymethyl group, butoxyethyl (1(4,1 (5 and R6 are the same as above), -5o2cc, -5O□B"
and -3O1H may be their quaternary salts, and the bases that can form quaternary salts with these °C are, for example, ammonia, pyridine, piperazine, piperidine, N~methylpyrrolidine, morpholine, diethylamine, Examples include trimedelamine.

The compounds of the present invention represented by the formula [+1] include compounds represented by the general formulas [[nl and [IV]].

0 N20 (In the formula, Y and I' are the same as above. Also, R8 represents an argyl group, a cycloalkyl group, a bitroxyalkyl group, or an alkoxyalkyl group.) (In the formula, Y, Y',
m' and no are the same as above. ) The method for producing the compound according to the present invention is shown below using the compound represented by the general formula [I[1] as an example.

(In the formula, I' and Ha are the same as above.) []N2 (1 That is, first, the compound represented by the general formula [II[-1]
Hereinafter, it will be abbreviated as compound [lll-1]. ) with a diazotizing agent in the presence of a base, the compound of the present invention in which Y is a hydrogen atom in general formula [I11] (hereinafter, compound [ll
1-2]. ) is obtained, and then the mixture is reacted with chlorosulfonic acid to obtain the compound of the present invention having the general formula rlII] in which Y is -502Cj/.

The cyanation reaction is usually carried out using a diazotizing agent in an amount of 0.5 to 3 mol, preferably 0.8 to 1.5 mol, per 1 mol of compound [I[[-1] and compound [1-1], and compound [I[-1] and compound [1-1]. ■
- 0.5 to 5 mol per mol per month, preferably 0.5 to 5 mol per mol.
8 to 1.5 mol of base in a suitable reaction solvent at -10 to
15 minutes to 5 hours at 30°C, preferably -5 to 10°C,
Preferably, the reaction is carried out for 1 to 2 hours.

Examples of reaction solvents used in the diazotization reaction include alcohols such as ethanol and isopropanol;
For example, ethers such as ethyl ether, isopropyl needle, detrahydrofuran, etc., halogenated hydrocarbons such as ceremonial nonalene, chloroform, tetrachloride, 2-dichloroethane, etc., such as n-hexane, cyclohexane, toluene, etc. Examples of diazotizing agents include p-)luenesulfonyl azide,
Examples of the base include pensene sulfonyl azide, 2-azido-3-ethylbenzothiazolium fluoroborate, and organic bases such as piperidine, triethylamine, N-methylpyrrolidine, N-methylmorpholine, pyridine, diethylamine, etc. Na(1(,Ill
, Nap(:2H5, MO(: (Gtl+) *
, KOC214=, alkaline earth metal sodium, sodium hydride, potassium hydride, and the like.

In addition, the chlorosulfonation reaction is performed on the compound [III-2
] Compound with lll-2] 1 to 1 O per mol
mol, preferably 2.5 to 4.5 mol of chlorosulfonic acid in the presence or absence of a solvent at -20 to 20°C, preferably -10 to 5°C, for 15 minutes to 5 hours, preferably What is necessary is just to make it react for 1 to 2 hours.

The reaction solvent used in the chlorosulfonation reaction is not particularly limited as long as it is an organic solvent that does not inhibit the chlorosulfonation reaction and is not likely to be chlorosulfonated itself; for example, carbon tetrachloride. , ethane tetrachloride, chloroform, 1,2-dichloroethane, halogenated hydrocarbons such as terene, carbon disulfide, etc. are usually preferably used.

If the Sθ□α body thus obtained is hydrolyzed, for example, by a conventional method, Y in the general formula [I11] is 15
In addition, if alcoholysis is performed instead of hydrolysis, the compound of the present invention having the general formula [1111, where Y is 15018'(R' is the same as above) can be obtained. can get. Furthermore, instead of hydrolysis or alcoholysis, the S02α form can be treated with ammonia, or, for example, monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, dimethylamine, diethylamine, dipropylamine, monoethanolamine, Aliphatic amines such as jetanolamine,
(In the formula, m' is the same as above.) Ketones and general formula compound [[1-1] are, for example, general formula (wherein, 1 represents an alkyl group, and m' is the same as above. ) and a ketone represented by the general formula (in the formula, 18 is the same as in ml) in the presence of, for example, metallic sodium, sodium hydride, metal alkoxide, etc., or Alternatively, it can be easily obtained by condensing an ester represented by the general formula (in the formula, R8 and H' are the same as above) with the presence of metal sodium, sodium hydride, metal alkoxide, etc. , it is sufficient to use what is obtained in this way.

Further, the method for producing the compound according to the present invention is shown below using a compound represented by the general formula [rV] as an example.

(In the formula, m゛ and no are the same as above.) ↓Chlorsulfonation In the formula 1, both l and 7' represent -502α, or one of them represents -5O□α and the other is a hydrogen atom. represents. Furthermore, m' and no are the same as above. ] That is,
First, when a compound represented by the general formula (IV-1) (hereinafter abbreviated as compound [rV-1]) is treated with a diazotizing agent in the presence of a base, Y and Yo in the general formula [■] are reacted.
is a hydrogen atom (hereinafter, compound [IV-2]
It is abbreviated as ) is obtained, and then this is reacted with chlorosulfonic acid to obtain the compound of the present invention, in which at least one of Y and Yo is 302α in formula [IV]. The reaction conditions for the diazotization reaction and the chlorosulfonation reaction may be carried out in accordance with the method for producing the compound of the present invention represented by the general formula [1111r] described above. The obtained 502Cf1. If the body is hydrolyzed, in the general formula [ ], Y, Y' or -SO, I+ (or one of Y and Yo is -5O, 11 and the other is -5O2α), or Y and Yo A compound of the present invention is obtained in which one of the atoms is -SO,11 and the other is a hydrogen atom. Also, instead of hydrolysis, alcoholysis may be used to produce Y or -5O,H'(R' is the same as above).

-5O,R'(11' is the same as above) (or Y and Y
Either o is 13o3n'(R') and the other is 1302CjL), or either Y and Yo are 130
A compound of the present invention in which 3R'(11') is the other hydrogen atom f is obtained. Furthermore, instead of hydrolysis or alcoholysis, the 5o2ct form can be treated with ammonia, or, for example, monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, dimethylamine,
Aliphatic amines such as diethylamine, dipropylamine, monoethanolamine, jetanolamine, etc., piperidine, piperazine, pyrrolidine, etc. can be used, so if you use the ones obtained in this way, you can obtain the legs.

Compound [IV-13 is, for example, a compound represented by the general formula (wherein Q represents a chlorine atom, a bromine atom, or an iodine atom, and mo is the same as above) and a compound represented by the general formula (wherein Q and no are the same as above) ) and 2,4-pentanone in a solvent such as cyclohexane, n-hexane, toluene, isopropyl ether, etc., for example, n-butyllithium,
Lithium diisopropylamide.

Lithium 1,1.1,3,3.3-hexamethyldisilazane, H/n-uLi, NaH/n-Bul,
It can be easily obtained by using a condensing agent such as i and reacting at a low temperature, for example, at IO or below.

Further, compound [IV-1] can be expressed by, for example, the general formula (wherein,
mo is the same as above. ) and Nisdel compounds represented by the general formula (where R and no are the same as above) in the presence of sodium metal, sodium hydride, metal alkoxide, etc. Since it is also easily obtained, one obtained in this way may be used.

The compound according to the present invention represented by formula [I] is 248.
High reactivity to 4 nm light. In addition, the resist using the compound according to the present invention has a large change in transmittance before and after exposure (approximately 50% or more), and the transmittance after exposure is also 7.
It is large, more than 0%. In addition, in a photosensitive material in which a photosensitive compound in the general formula rI], which is a functional group capable of reacting with a resin (x (or/and progresses, which has the effect of reducing the solubility of the resin in the developer. Therefore, by using this as a material for a resist or the like, a well-shaped resin pattern can be obtained.

That is, the structure according to the present invention is represented by the general formula [11]. Therefore, it is desirable that the photosensitive material can suppress the alkali i+) solubility of the novolak resin and the like in the unexposed areas.

In the photosensitive compound according to the present invention in which X (or/and xo) in formula [i] is a functional group capable of reacting with a resin, the terminal group has, for example, -502α.

-5O2Br, -5o3H, -coall, -GO
Since it contains functional groups such as CI, -C (lBr, -Nl2, etc.), it can be heated to form an alkali-soluble part of the resin, such as a monomer group, by UV light, for example, by excimer laser. Therefore, the photosensitive material of the present invention becomes alkali +7 soluble only in the light-irradiated portion, and becomes a so-called positive type material.

However, general positive resist materials are a combination of a photosensitive material, a resin, and a solvent, and because alkali-soluble novolac resins are mainly used as the resin, crosslinking progresses and it is difficult to suppress the alkali +7 solubility of the resin. can. Therefore,
When used in photosensitive materials, the problem of film thinning in unexposed areas can be significantly improved.

In addition, the photosensitive material -Cυl according to the present invention represented by the general formula II]
The substitution position of the substituent such as lr, -Nil, etc. on the benzene ring and the substitution position in the compound of the present invention represented by the general formula [111] may be at the o-, m-, or p-position with respect to the methylene group. However, there is no difference in the effect as a photosensitive material in either case. Furthermore, regarding the length of methylene 1n, no matter how many natural numbers m and n are, or whether m' and n' are integers from 1 to 20, there is no big difference in the effect. However, since photosensitive compounds with long methylene chains generally have low solubility in alkaline developing solutions, high dissolution inhibiting ability can be obtained even when used in small amounts. Therefore, it is possible to increase the concentration of the developer, and it is possible to stabilize the development conditions. However, if the methylene chain is too long (e.g. compounds larger than 20), the solubility in the solvent will be poor and it will be difficult to dissolve it at a concentration that has practical dissolution inhibiting ability and photosensitivity. It is preferable that the length be long enough to avoid poor solubility.

In addition, resins used in positive resist materials and 17
For example, baracresol/novolac resin, metacresol/novolac resin Jli, orthochlorometacresol/novolac resin, maleimide resin, hydroxystyrene resin, poly(paravinylphenol) resin, phenolic resin, styrene resin, maleic acid resin, etc. 24
Examples include alkali 1R-soluble resins with good light transmittance of around 8.4nra, and the mixing ratio of these resins and the photosensitive compound according to the present invention represented by general formula [1] in a positive resist material. is 1 to 0.05 weight, preferably 0.15 weight of the photosensitive compound according to the present invention per 1 weight of resin.
When the ratio of resin to photosensitive compound according to the present invention is 1:0.15, the resist material has the highest reactivity to light and a resist pattern with the best aspect ratio can be obtained.

Further, the above resist materials are usually used after being dissolved in an organic solvent, and examples of organic solvents used for this purpose include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethyl cellosolve acetate, methyl cellosolve acetate, etc. However, the solvent is not limited to these, and any solvent that can dissolve the photosensitive compound and resin may be used.

Pattern formation using a resist material containing the compound according to the present invention may be performed, for example, as follows.

The resist material containing the compound according to the present invention is coated on a substrate such as a silicon wafer to a thickness of about 0.5 to 2 μm.
~0.5 μm) and heat it in the oven at 70~110℃.
70°C for 10-30 minutes or on a hot plate.
Brebake at ~110°C for 1-2 minutes. Next, a mask for forming a desired pattern is held over the above resist film and exposed to deep ultraviolet light of 300 nm or less.
(exposure dose)20~300mJ/c
After irradiating to about m2, using a developer such as 0.1% tetramethylammonium hydroxide (TMΔH) aqueous solution for about 0.5 to 3 minutes, immersion method, paddle method, spray method, etc. When developed by a conventional method, a desired pattern is formed on the substrate.

Furthermore, a resist material containing the compound according to the present invention can also be used as a contrast-enhancing material.

That is, for example, a suitable resist material (e.g. MP2400
(manufactured by Sibley)) to a thickness of about 0.5 to 2 μm on a substrate such as a silicon wafer, and then heat it in an oven at 70 to 110°C for 10 to 30 minutes or on a hot plate. After baking at 70-110°C for 1-2 minutes, a contrast enhancing material containing the compound according to the present invention is further applied thereon to a thickness of 0.1-0.
Apply to approximately 5 μm. Next, a mask for forming a desired pattern is held over the above resist, and deep ultraviolet light of 300 nm or more is applied at an exposure dose (expo
After irradiating the pattern at a dose of about 1.5 times that when forming a pattern using only the lower layer resist, a developer such as a 20% aqueous solution of 240I developer (manufactured by Sibley) is used. By developing for about 5 to 3 minutes by a conventional method such as a dipping method, a puddle method, or a spray method, a desired pattern is formed on the substrate.

In addition, the developing solution used in the various pattern forming methods described above is such that, depending on the solubility of the resin used in the resist material in an alkaline solution, it hardly dissolves the unexposed areas and dissolves the exposed areas. All you have to do is select an alkaline solution with an appropriate concentration, usually 0. Selected from the range of old to 50%. In addition, the alkaline solution to be used includes, for example, amines such as 1MAH, for example, NaO
Examples include solutions containing inorganic alkalis such as H and KOII.

The present invention will be described in detail below with reference to reference examples and examples, but the present invention is not limited in any way by these.

〔Example〕

Reference example 1. Synthesis of p-h luenesulfonyl azide (tosyl azide) 22.5 g (0.35 mol) of sodium azide was dissolved in a small amount of water, and then diluted with 90% ethanol (130%). Next, an ethanol solution in which 60 g (0.32 mol) of ρ-toluenesulfonyl chloride was dissolved was added dropwise at 10 to 25°C, and the mixture was stirred and reacted at room temperature for 2.5 hours. The reaction solution was concentrated under reduced pressure at room temperature, and the residual oil was washed with water several times and then dried with anhydrous ggso. Remove the desiccant and
50.7 g of p-toluenesulfonyl azide was obtained as a colorless oil.

'tlNMR15pprB(11:Dα,,): 2
．． 43 (:lH,s,elLL), 7.24(2
H, d, J-811z, phenVI-G'l+ c
5), 7, 67 (2II, d, , 1-1l
Hz, pl+enyl-C2,C:,,).

l1l (Neat): 2120cm” (-N3)
.

Reference Example 2. Synthesis of 1.7-sipheny-3.5-hebutanedione 17 g of 60% sodium hydride was charged in 200 ml of cyclohexane, and 37 g (0.37 mol) of acetylacetone was dissolved therein at 20 to 25°C to create a cyclohexane solution. was added dropwise, and the mixture was stirred and reacted at the same temperature for 40 minutes.

Next, after injecting 91.8 g of N,N,N',N'-tetramethylethylenediamine, 337 g of a 1.6M n-hexane solution of n-butyllithium was added dropwise at -5 to 0°C, and the temperature was further raised to room temperature for 24 hours. Made it react. Next, 93.7 g of benzyl chloride was added dropwise to this reaction solution at 0 to 5° C., and after standing overnight, the solution was poured into dilute hydrochloric acid. The organic layer was separated by standing, washed several times with water, and then dried over anhydrous MgSO4.

After removing the desiccant, the solvent was distilled off to obtain 79 g of a red oily substance, which was distilled under reduced pressure to obtain bp, 185-190'C10,4.
23.5 g of 1,7-diphere-3.5-butanedione of the Ig fraction (+nm) was obtained as a pale yellow oil.

Example 1.1.7-bis(4-chlorosulfonylphenyl)-4-diazo-3,5-hebutanedione (general formula [
rV], Y = Y'・-3O2Ce, m'-
Synthesis of compound with n'=2) 11) 4-diazo-1,7-
Synthesis of diphenyl-3,5-heptanedione 1,7-diphenyl-3,5-heptanedione obtained in Reference Example 2 16. tig (60 mmol) was dissolved in 120 Tnl of methylene chloride and 5. Reference example with addition of Ig (60 mmol) at 0-5℃! 2.4 g (63 mmol) of p-)luenesulfonyl azide obtained in step 1 was added dropwise, and the mixture was further stirred and reacted at the same temperature for 2 hours. After washing the reaction solution with a dilute caustic potash aqueous solution, it was washed several times with water and anhydrous M)JS
Dry with O4. After removing the drying agent, the solvent was distilled off to obtain 19 g of a reddish-orange oil. The residual oil was then separated by column separation [silica gel: Wakogel G-200 (manufactured by Wako Pure Chemical Industries, Ltd.)]
, Eluent: methylene chloride, 4-diazo-1,7-diphenyl-3,5-hebutanedione, 8. Og was obtained as slightly yellow crystals. mp, 62.5-64.0°C.

'HNMIIδppm((:D(f,,): 2.9
7 (811,s, -[;%-X 4), 7.20 (1
0fl, s, aromatic ring x 2).

In(Kllr-disk) + 2120cm-'(
-N2), 1650cm-' (CJ).

C211,7-bis(4-chlorosulfonylphenyl)
Synthesis of -1-diazo-3,5-hebutanedione 4-diabu obtained in (1) 1.
Fudiphenyl-3,5-hebutanedione 7.5g (2
A chloroform solution in which 4 mmol) was dissolved was added dropwise at 0 to 5°C, and the mixture was stirred and reacted at the same temperature for 1 hour. The reaction solution was poured into 0.54ml of ice water, extracted with chloroform, and the separated chloroform layer was washed with water several times and then dried over anhydrous Mg504. After removing the desiccant, the solvent was distilled off to leave a residue of 5 g of orange oil.
I got it. The oil was then separated by column [silica gel: Wakogel G-200, dissolved! y &: n-hexane/'methylene chloride = 3/I - + l/I (V/V) ] L/
, 1,7-bis(4-chlorosulfonylphenyl)-4
3.0 g of -diazo-3,5-hebutanedione was obtained as yellow crystals. mp, ]21-122.5°C.

Direction II N M 11 δpl)m(CD(J! 3
) : 3.10 (a skin s, -(:%
-X 4), 1 old KBr-disk): 2130
cm-' (-N2), 1540cm-' ((:J)
.

Elemental analysis value ((:+J(+eα2 N 206 S
2) Theoretical value: c*, 45J4: HJ: 1.2
0; N*, ! i,! 'i7゜Real d: 11 value: C tree, 45.25; H*, 3.36: N'J4
．． ! i, 56° Example 2, I, 7-bis(4-
ethoxysulfonylphenyl)-4-diazo-3,5-
Hebutanedione (in the general formula [rV], Y = Y'
1,7-bis(4-chlorosulfonylphenyl)-4-diazo-3,5- obtained in (2) of Example 1 700 mg (1.4 mmol) of hebutanedio'y was dissolved in 15 ml of ethanol and 10 m6 of methylene chloride, and 420 mg of triethylamine was added dropwise thereto at 5-10°C. After reacting with stirring at room temperature for 8 hours, it was concentrated under reduced pressure, the residue was diluted with 40-methylene chloride, and after washing several times with water, anhydrous Mg5
It was dried with CJa. After removing the desiccant, the solvent was distilled off, and the remaining crude oil (820 mg) was separated on a column [silica gel: Wakogel G-200. Eluent: n-hexane/ethyl acetate = 5
/1-Th 3/l (V/V) l 1,7-bis(4-ctoxysulfonylphenyl)-4-diazo-
450 mg of 3,5-hebutanedione was obtained as a slightly yellow viscous oil.

'IINMRδppm(CD(f,,):I,3
1 (611,t, J-7Hz, SQ,, C112Cy
x 2), :J, 08 (8fl, bs, -CD
, CD, co-x 2), 4.12 (411゜q, J=
711z, 5O3 (jj, Cl13x 2), 7.
41 (411, d, J-8Hz.

phenyl-C2, (:6X2), 7.83 (4
11,d, J・8Hz, phenyl-c,,C
,,x2).

IR (Neat): 2130cm-'(-(:N2
), 1650 cm-' (C=O).

UV (CIl, CN) λmax (ε): 229.
Onm (41880).

Elemental analysis value (G23H26N208S2) theoretical value: C
! t, 52.86. H! 5.01: N
! 5.36° Actual value: C%, 52.65;
8%, 5.21; N*, 5. :Jl.

Example 3. I, 7-bis(4-N,N-diethylaminosulfonylphenyl)-4-diazo-3,5-hebutanedione (in general formula [IV], Y=Y'=-5O2N
Synthesis of (f; Js) 2 , m'・no・2 compound) t,7-bis(4-chlorosulfonylphenyl)-4-diazo-3,5-heptane obtained in (2) of Example 1 700 mg (1.4 mmol) of dione was dissolved in acetonitrile 15
It was dissolved in Fnl and N,N-diethylamine tg was added dropwise at 5-10°C. The reaction mixture was stirred at room temperature for 10 hours, concentrated under reduced pressure, and the residue was diluted with 40 ml of methylene chloride, washed with water several times, and dried over anhydrous MgSO4. After removing the desiccant, the solvent was distilled off, and 800 mg of the crude oil residue was transferred to column B.
[Silica gel: Wakogel C-20-0. Hina 7 nights: n
-Hexane/ethyl acetate = 5/1 → 3/I (V7V)
] L,1,7-bis(4-N,N-diethylaminosulfonylphenyl)-4-cyaso-3,5-hebutanedione 370B was obtained as a slightly yellow viscous oil [7].

11NMRδppm ((:DCL+): 1.13
(12N, t, J=711z, N-C!l.

CshiX4), 3.05 (811, bs, -%%C0-X
2), :1.2:1 (811゜q, J・711z, N
-Cjj, C13X4), 7.34 (4N, d, J=
81z, phenyl-C2, C6x2), 7.73
(4B, d, J=811z, phenyl-C3,C
,,x2),.

1ll(Neat): 212Ucl'(-(:N2
), 1650 cm-' (G=0).

UV (1; II, GN) λmax (ε): 2:1
4.4nm (38160).

Elemental analysis value (C27+136N40R52) theoretical value:
C'<, 5fi. 23. H'4.6.29,
N'! , 9.7+.

Actual value: C tree, 56.40: H tree, 6.42
, N! ! , 9.60° Example 4.1.7-Bis(4
-sulfophenyl)-4-diazo-3,5-hebutanedione (in general formula [IV], Y"Y'=-5(h)
1,7-bis(4-chlorosulfony,luphenyl)-4-siacy-3,5-heptanedione obtained in (2) of Example 1. Og (4.0 mmol) in acetonitrile 70
The mixture was mixed in 50ml of water and stirred at 30-35°C for 25 hours.

After the reaction, it was washed three times with 30 rnl of methylene chloride, the aqueous layer was reduced and concentrated, and 1,7-bis(4-sulfophenyl)-
1.6 g of 4-siacy 3.5-hebutanedione were obtained as a pale yellow viscous oil.

'IINMRδppm (Dαj-DMSO-d6):
2.85 (4tl, t, J・7Hz.

C) 12cjl, Go-x 2), :3.08(4
tl, t, J=711z, 8r-CjjlC112(:
0-X 2), 5.32 (2tl, bs, So, I
I x 2), 7.21 (411, dl=8Hz.

phenyl-3. C,,X2), 7.54(41
1, d, J=8Hz, phenyl-C2, (:,
X2).

l1l(Neat): 2110cm-' (-N
2), 1635cII]-' (C=0).

Elemental analysis value (NI+JI+5N208S2) Theoretical value: C
Turtle, 48.92.8! Ii, 3.89; N!
6.0+.

Actual value: C96, 49, 20; H! On 4.15
; N*, 5.79° Example 5.1.7-bis(
4-sulfonatophenyl)-4-diazo-3,5-hebutanedione diammonium salt (in the general formula [IV], a compound of YY“-so”Ju4゜+n′・n゛・2) 1,7-bis(4-sulfophenyl)- obtained in Synthesis Example 4 of
4-Thiaso 3.5-hebutanedione 700B (1,5
Dissolve 2 mmol) in acetonitrile 2 (7 mmol) and knead 0
0.4 g of 28% ammonia aqueous solution was added dropwise at ~5°C, and the mixture was stirred at the same temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and the residue was washed with acetonitrile several times and dried under reduced pressure to give 1.7-bis(4
-sulfonatophenyl)-4=thiaso3.5-hebutanedione diammonium salt 650+nH was obtained as a slightly yellow viscous oil.

11HMIIδPpm((:D(f3-DMSO-d6
3: 2.84 (4H, t, J-7H2°-Ctld
:0-x2n, 3.08(4H,t,J-7
Hz, Ar- to 112- x2) 4.04 (8H, b
s, -WH,X2), 7. l8 (411, d, J=8t
(z, phenVl-C,,l;6x2), 7.52
(4tl, d, J-811z, phenyl-
C3, CsX2).

11t (Neat,): 3:lOOcm-' (-
NH4), 2]10cm-' (-CN2).

1620cm-' (CJI.

Practical example 6, l, 7-bis(4-sulfonatophenyl)-4-diazo-3,5-heptanedione ditriethylammonium salt (in the general formula [■], y-y'
-5oH stomach 11 (C2H5)3. m'sn's2 compound) obtained in Synthesis Example 4! , 7-bis(4-sulfophenyl)-
700 mg of 4-thia'j'-3,5-heptanedione (
1.5 mmol) was dissolved in 20°C of acetonitrile, and 0.6 g of triethylamine was added dropwise thereto at 0 to 5°C.
The mixture was stirred for 3 hours at the same quality. Concentrate the reaction solution under reduced pressure to remove the residue.
After washing with acetonitrile several times and drying under reduced pressure, 1,7-his(4-sulfonatophenyl)-4-diazo-3,5-
Hebutanedione di-ethylammonium salt 900
mg as a pale yellow viscous oil.

'IIN)4Rδppm(CDCl2-DMSO-d,
): 1.16 (18H, t, J-711z.

N-G1121; ILLX 61, 2.84 (4tl
, L, J=7tlz, -(:jlCt)-X2)
.

:J, 04-3.12 (1611, +n, N-[1:
H, el13X6 and Ar-G%-x2), 3.49
(2H, bs, 'Ntlx2), 7.18 (411,
d, J-8Hz.

phenyl-C2, fl:6X2), 7.51 (4
11,d, J・811z, phenyl-1:,,
I:5X2).

18(Neat,): 2110cm-'(-(
:N2), 1650cm-'(C-0).

Reference example 3, 1. Synthesis of Traphenyl-4,6-Tunanthione 43 g of 60% sodium hydride was placed in 510 ml of cyclohexane, and a cyclohexane solution containing 9:1.8 g (0.0 g, 4 dry l) of acetylacetone was added dropwise to the dough at 20-25°C. 3 and stirred and reacted at the same temperature for 40 minutes.
゜ Next, after injecting 1.2 g of N,N,N',N'-tetramethylethylenediamine 2:I, n-
85 figs of a n-hegisan solution of butyl lithium was added dropwise, and the temperature was further raised to room temperature and reacted for 24 hours. Next, 405 g of β-phenethyl bromide was added dropwise to this reaction solution at 0 to 5° C., and the reaction and post-treatment were carried out in the same manner as in Reference Example 2 to obtain 350 g of a reddish-brown oil. Column molecules are stiff
[Silica gel: Fuco-gel C-200, solution: benzene] and 1,9-diphenyl-4,6-butanedione 6
6, '1 g was obtained as a pale yellow oil.

11HMI (δppm (COα, ): 1.85
~1.97 (4H,m,-(:It,(:H□1:
0-X 2) , 2.27 (411,t,,J□
8Hz, -GH2Gll, GO-X2).

2.62(411,t,,I=8Hz,8r-(:If
, ell□-x2), 3.43 (211,s.

Knoll type 5 melody), 7.10~7.33 (108,
m, aromatic ring x 2).

15.5:l (IN, bs, -0ff (enol)),.

l11fNeat): 1725cm-', 17
00cm-', 1610cIff-'Example 7.1
．． Synthesis of 9-bis(4-chlorosulfonylphenyl)-5-diazo-4,6-nonanedione (general formula % formula % compound) (1) Synthesis reference of 5-cyaso 1,9-diphenyl-4,6-nonanedione 60 g (0,195 mol) of 1,9-diphenyl-4,6-nonanedione obtained in Example 3 was mixed with 27 g (0,195 mol) of methylene chloride (
7 and 19.8 g of triethylamine (0,19
P-1 obtained in Reference Example 1 at 0 to 5° C.
40.1 g (0,203 mol) of luenesulfonyl azide was added dropwise, and the mixture was stirred and reacted at the same temperature for 2 hours. After washing the reaction solution with a dilute caustic potash aqueous solution, it was washed with water several times to obtain anhydrous Mg.
Dry with SO4. After removing the desiccant, the solvent was distilled off to obtain 6.8 g of reddish brown crystals. Then, it was recrystallized from ethanol to give 5-diazo-1,9-diphenyl-4,6-nonanedione 1. Og was obtained as pale yellow flaky crystals. mp, 54
．． 5-56.5°C.

'IINMRδppm (CDα3): 1.9:l
~2.04 (4tl, m, -f:H1CII2GO-
X 2), 2.65-2.75 (8tl, m, A
r-GIX[;H2GH2(:0-X2), 7.14
~7. :11 (1011, m, aromatic ring x 2).

1tl (Kllr tablet): 2080cm-'(-CN
2), 1640 cm-' (C=0).

(211,!]-bis(4-chlorosulfonylphenyl)-5-diazo-4,6-nonanedione (general formula [IV
], the synthesis of Y-Y'-3O2α, a compound where m' = 3) was carried out using 60. (21 5-diazo-1,9-diphenyl-4,6-nonanedione obtained in (1) in 1 g)
．． A chloroform solution containing 5 g (64,: j mmol) was added dropwise at 0 to 5° C., and the reaction and post-treatment were carried out in the same manner as in Example 1 (2) to obtain 10 g of a crude oil. Column fraction M [Silica gel: Wakokel C-20]
0, Eluent 20-hexane/'methylene chloride = 1/1→
l/II (V/V) ] L,, 1.9-bis(4-
6.8 g of chlorosulfonylphenyl)-5-diazo-4,6-nonanedione were obtained as a yellow viscous oil.

'HNMI (δppm (CDC9: 1.98~2
．． 1:, 1 (4H, m, -Gjj, C112GO-X
2), 2.71i ~ 2.89 (8N, m, Ar
-(:!hC112C1f, GO-X2), 7.4
! 1 (4H, d, J=8Hz, pt+enyl-C2,
f16X2), 7.97 (411, d, J□811
z, phenyl-C3j; 5x 2).

[R (Neat): 2110cm -Bird (-C
N2), 1650 cm-l (C”0).

tJV (N to CI+3) λmax (ε): 24
4.2Nm (33450).

Elemental analysis value (1; 2 + 112° (f 2 N 206
S2) Theoretical value: C! ! , 47.46. H96
,3,79: N! Ii, 5.27°actual d1 value:
C! , 47.39: H%, 3.96; N'
! , 5.33゜Example 8.1.9-bis(4-methoxysulfonylphenyl)-5-diazo-4,6-nonanedione (in general formula [IV], Y -Y'□-50,
Ct13. Compound of m'=n'□3) Synthesis of Example 7 (1,9-bis(4-chlorosulfonylphenyl)-5-diazo-4,tononanedione 1 obtained in 21)
Add 420 Bf of triethylamine to a solution of 100 mg (1.5 mmol) dissolved in 16 methanol and 10 methylene chloride at 5-10°C. -dropping, dripping, fruit/
The reaction and work-up were carried out in the same manner as in Example 2 to obtain 700+ ng of a crude oil. This is separated by column [silica gel:
Wakogel G-200. Eluent: n-hexane/ethyl acetate = 5/1 → 3/I (V/V), 1 L, 1,9
350 mg of -bis(4-methoxysulfonylphenyl)-5-diazo-4,tononanedione was obtained as a slightly yellow viscous oil.

'llN11llllδppm (CDα3): 2.
02 (411,q, J=811z, -GH,,elf
0-X2), 2.77(81(, L, J=8fl
z, -(NijiGlf2(:If, GO-X 2).

3.75 (old 1.s, 5O31; if, X 2),
7.39 (411, d, J=IIHz, phenyl
-(:,,C6X2), 7.8:t(4fl, d,
J=811z, phenyl-C3j:5X2).

In(Neat): 2110cll(-CN2),
1645clI+-' (C=0).

UV (N to C1+3) λmax (ε): 22
8.3Nm (39110).

Elemental analysis value (CzfflhJ20,1S2) Theoretical value:
C'4.52.86. H%, 5.01: N
*, 5.36°Actual measurement &I: C*, 52.73;
H! 5.19, N! 5.22゜Example 9.1.9-bis(4-sulfophenyl)-5-diazo-4,6-nonanedione (in general formula [IV],
Y-Y'-3fl, tl, m'=n'-3 compound)
Obtained in Synthesis Example 7! , 9-bis(4-chlorosulfonylphenyl)-5-diazo-4,6-nonanedione 5g
f5.6 mmol) in acetonitrile 100 mI! and 70 rnl of water, followed by reaction and post-treatment in the same manner as in Example 4 to obtain 2.0 g of 1,9-bis(4-sulfophenyl)-5-diazo-4,6-nonanedione.
was obtained as a light brown viscous oil.

'INMI(δppm(DMSO-d6)): 1.7
8-1.89 (4H, rn, -el12C%C11
2GO-X 2), 2. [11(4)1. t, J-
7,511z, -GHzLO-x2), 2.76(
4H, t, J□7.5tlz, Ar-(:H, C1l□
-x 2), 4. Ifl (2H, bs, -5O Tsuji
), 7.18 (411, d,, I・7.5Hz, ph
enyl-c,,c,X2), 7.54(4fl,d
, , 1-7.5tlz, pt+enyl-Czl;
6×2).

l11(Neat): 2150cm-'(-CN2
), 1640 cm-'((>0).

Elemental analysis value (C2+)I2J20gS2) Theoretical value:
C%i, 51.00; H! 4.48; N
'4.5.66゜Actual value: C$, 50.9+,
H*, 4.63: l, 5.79° Example 10
．． 1.9-bis(4-sulfonatophenyl)-5-diacy4,6-nonanedione ditriethylammonium (in the general formula [rV], Y=Y'・-3O3NH(
GJs)3. Il! Synthesis of compound '-n'''3) 1,9-bisthrosulfophenyl obtained in Example 9
-5-thiaso 4.6~nonanedione 1.75g (3,
54 mmol) and 0.75 [triethylamine] were stirred in 20 ml of acetonitrile at 20-25°C for 3 hours. After the reaction, the residue was concentrated under reduced pressure, washed several times with acetonitrile, and dried under pressure to give 1,9-bis(4-sulfonatophenyl)-5-diazo-4,6-nonanedione ditriethylammonium 2. .2: Ig as a slightly yellow viscous oil 1);

Direct HN M RδI)pm([1M5O-dfi):
1.17 (1811,t, J=7.511z.

N-(:II, l:lI*x6), 1.76-1.8
8 (411, m, -Cjj, H2GO-X2), 2
．． 60 (4tl, t, J・7.7flz, -1; 112
CO-x2), 2.74 (4N, t.

J=711Z, Ar-Cjj, -X2), 3.08
(1211,q, J-7,5Hz.

N-f; 1I2f:113X6), 1. :17(21
1, bs, N■X2), 7.15 (411゜d, J
=)llIz, phenyl-C2, Ct, x2),
7.52 (411, d, 1-8) 1z.

phenyl-C3J:5X 2).

It((Neat): 2700cm-', 215
0cl', 1700cm-'1640cl' Elemental analysis value (G3311s2Na08S2) theoretical value:
C! 56.87; 8%, 7.52 7 N'
! , 8.04゜Real-111Idi: CL
56.61: 8%, ? , 83: N
'? ,, 8.29゜Reference Example 4.1.1 Synthesis of 3-diphenyl-6,8-tridecanedione (1) Synthesis of 4-phenylbutanol Lithium aluminum hydride 67. 2 g of 4-phenylbutyric acid was added thereto and suspended, and a tetrahydrofuran solution in which 225 g (1:37 mol) of 4-phenylbutyric acid had been dissolved was added dropwise at 15 to 25° C., and the reaction was further stirred at room temperature for 1 hour. After the reaction, ice water 3.
Q and 200 g of sulfuric acid, and extracted with ethyl acetate. After drying the ethyl acetate layer over anhydrous MgSO4, the solvent was distilled off, and 227 g of the residue was distilled under reduced pressure, bp, 113-115°C, 70
．． 4-phenylbutanol 191 of 5m+n11g fraction
g was obtained as a colorless oil.

(2) Synthesis of 1-chloro-4-phenylbutane 300 g of thionyl chloride was added dropwise to 189 g (1,26 mol) of 4-phenylbutanol obtained in [1) at room temperature, and then
Stir and reflux for hours. After concentrating the reaction solution.

The residue was distilled under reduced pressure, bp, 122-123°C, 717 mm1
149 g of 1-chloro-4-phenylbutane from the g fraction was purified as a colorless oil.

Synthesis of (311,13-diphenyl-1i,8-)lysocandione 7 g of 60% sodium hydride (oil-based) IO was suspended in 140 ml of cyclohexane under a nitrogen atmosphere, and 2,4-pentanedione 26 .7g (0,2
A solution of 67 mol) in cyclohexane was added dropwise at room temperature, and the mixture was further stirred for 2 hours. Furthermore, 34.1 g of N,N,N',N'-tetramethylethylenecyamine was then added to 185ml of n-butyllithium (1,6M n-hexane solution).
It was added dropwise at ℃. After stirring at room temperature for 2 hours, 1IOg of 1-chloro-4-phenylbutane obtained in (2) (0,65
mol) and then at room temperature! The reaction was allowed to proceed for 2 hours. The reaction solution was poured into 1 liter of ice water, neutralized with five drops of diluted hydrochloric acid, and extracted with ethyl acetate. The separated ethyl acetate layer was washed with water and then dried with anhydrous MgSO4. After removing the desiccant, the solvent is distilled off and the residue is divided into columns. ! [Silica gel: Fucogel C-
200, Eluent: Benzene/n-hexane = 4/I+
10/l (V/V)] 1.13-Schiff x Knee
2.5 g of Ru-6,8-tridecanedione was obtained as a pale yellow oil.

11 N M Rδppm ((:Dα31 : l
, 26-1.42 (4N, [11,-CHzCH2(
:ll□ni(]-x2), 1.56~1.69(81
1,m, -C%C1hG%Cl12G.

x2), 2.26 (4N, t, J=BHz, -CI1
2CH2COClh X2) 2.61 (41-1, t
, J411z, 8r-C%-x2), 3.52
(2H, s, -CO nor type 415), 7.15-7
．． 30 (1011, +n, aromatic ring x 2).

15.52 (IN, bs, 0 old engineer l-ru)).

IR (Neat,): 1700cm-', If
ioocm-'real h'' 6 examples 11.1.13-bis(4-
chlorosulfonylphenyl)-7-cyacy6,8-tridecanedione (=in the general formula [rV], Y-Y'-
Synthesis of compound (5O□α5m°=n°=5) (1) 7-diacy1,13-diphenyl-6,8-)
1,13-diphenyl-6,8 obtained in (3) of Synthesis of Lysocandione Reference Example 5
- 2.0 g (5.5 mmol) of dolidecanedione was dissolved in 1 ml of methylene chloride, and 470 mg (470 mg) of piperidine (
After adding 5.5 mmol), 1.14 g (5.8 mmol) of p-toluenesulfonazide obtained in Reference Example 1 was added dropwise at 0 to 5°C. The reaction and post-treatment were carried out in the same manner to obtain 2.8 g of a brown oil.
o o.

Eluent: n-hexane/ethyl acetate 4/1 (V/V
) ]7-diacy1.13-diphenyl6.8
- Tridecanedione 1.9 g were obtained as a pale yellow viscous oil.

'HNMI(δppm(CDα3): 1.34~
1.43(411,m,-(:jj2Gf12(:11
2GO-X2), 1.58 to 1.73 (8H, m, -
(:H2ClI2%C112GO-X 2), 2.
57-2.64 (4tl, m, -i:1I2Cjjl
GO-X 2), 2.67-2.74 (4119m
, Ar-(:H,-X2), 7.14-7.30(
IOH, m.

Aromatic ring X2).

In(Neat): 2100cm-'(-CN2)
, 1650 cm-' (G=0).

(211,1: I-bis(4-chlorosulfonylphenyl)7-cyacy6,8-tridecanedione (general formula %
Formula % 7-Diacyl 1,13-diphenyl-6,8-tridecanedione obtained in (1) in 3.7 g of lylorsulfonic acid
A chloroform solution in which 1.6 g (4 mmol) was dissolved was added dropwise at 0 to 5°C, and the reaction and post-treatment were carried out in the same manner as in 12) of Example 1 to obtain a crude oil 800B. This was separated by column separation [silica gel: Wakogel C-200,
Eluent: n-hexane/ethyl acetate・2/141/l
(V/V month) 300 mg of 1,13-bis(4-chlorosulfonylphenyl)-7-cyacy6,8-tridecanedione was obtained as a slightly yellow viscous oil.

11NMRδ9pm (CDCft3): 1. +9~
1. :15 (4H, m, -eliel120H, 0
-x2), 1.51 to 1.94 (12)1. rn
, -8%-X6).

2.70~2.77 (4tl, m, ^r-G:l1
l-x2), 7.41 (4H, d.

, I・8.5Hz, phenyi(:2.C:,X2)
, 7.95(411,d,,h8.511z.

phenyl-C2, Csx 2).

IR (Neat): 2160cm-'(-CN
), 1650cm - Emperor (C-O).

1:170cm-' (502).

Elemental analysis value (G2q1128G12N20cS2) Theoretical value: C! %, 51. +1. H! li, 4.80
: N! %i, 4.77°Actual value: Cf, 5
0.83; H! ti, 5.06; N%i, 4
．． 58° Window Example 5. Synthesis of 1-phenyl-2,4-pentanedione 600 g (6 moles of 3,1i) of ethyl phenylacetate and 70.7 g (1,22 moles) of acetone were charged.
! , :, 28g of sodium at 10-40 (1,22
atoms) were added slowly. After further stirring for 1 hour at 30 to 40°C to dissolve, the mixture was reacted at 70 to 80°C for 4.5 hours. After the reaction, 1.2 Il of water was added, and diluted hydrochloric acid was added dropwise for neutralization, followed by extraction with chloroform. The separated chloroform layer was washed with water and then dried with anhydrous MgSO4.

The desiccant was removed and the solvent was distilled off to obtain 515 g of a reddish brown oil. Then, the residue was distilled under reduced pressure to bp 142-146℃/
53.2 g of 1-phenyl-2,4-pentanedione of a 15 mn+lIg fraction was obtained as a colorless oil.

Example 12. 1-(4-chlorosulfonylphenyl)
-3-Diazo-2,4-pentanedione (general formula % formula %
) 16.2 g (0.21 mol) of l-phenyl-2,4-pentanedione obtained in Reference Example 5 was dissolved in 50 methylene chloride.
0 ml of P-toluenesulfonyl azide 4C obtained in Reference Example 1 was added dropwise at 0 to 5°C to which 17.5 g (0.21 mol) of piperidine was added, followed by further addition at the same temperature. The reaction was carried out for 1 hour. The reaction solution was washed with a dilute aqueous caustic potash solution, washed with water, and dried over anhydrous Mg504. After removing the desiccant, the solvent was distilled off to obtain 50 g of a brown oil. Then, the residual oil was separated by column (silica gel: Fuco-gel C-200, elution: n-hexane/ethyl acetate = 10/l (v/v)) L/, 3-thiaso 1
-Phenyl-2,4-pentanedione33. flg was obtained as an orange-red viscous oil.

'IINMII δ1) pl[l(to D to I,):
2.36(3H,s, (:H,), 4.00(2+
1. S, -(:lI,-), 7.23(511,s
, aromatic ring).

IROJ ean) 2 2141) cm-'(-
N2), 1660 cm-' (N=0).

Synthesis of (211-(4-chlorosulfonylphenyl)-3=cyaso-2,4-pentanedione) 3- obtained by il+
Thiaso 1-phenyl-2,4-bentanedione 16.
5g (82 mmol) of chloroform 50rn1! 38 g of chlorosulfonic acid was added dropwise to the solution at -15 to -10°C. After stirring for 2 hours at -15 to -10°C, 10 to 15
The reaction was continued for an additional 3 hours at °C. The reaction solution was poured into 1.5 ρ of ice water, extracted with chloroform, and the separated chloroform layer was washed with water and dried over anhydrous Mg5O. After removing the desiccant, the solvent was distilled off, and the remaining 20 g of reddish brown oil was separated by column (silica gel: Wakogel C-200, solution: n-hexane/ethyl acetate = 5/l (V/V)) L /,
10 g of a reddish brown oil was obtained, which was recrystallized from ethyl ether to give 1-(4-chlorosulfonylphenyl)-3-
4.0 g of diazo-2,4-bentanedione was obtained as yellow prism crystals.

mp, 84.0-86.5°C (dec,).

'IINMRδppm (CDI:I,): 2.45
(Fll,s,-Cjj,,), 4.30(2
11,s, -(Hl-), 7.54 (211,
d, J=811z, pheny 1-C2, C6)
.

8.00 (211, d, J-1t) lx, phenyl
-(3,1;5).

10 (Br-disk): 2125cm-'(-
N2), 1860 cm-' (C=O).

Elemental analysis value (G+ +1IqCIN20.+S) Theoretical value: C%, 4:1.94; 8%, :1.02: N%
,9. :12° Actual value: C*, 44. O2, N96,
3. I4; N! 9.30°Reference 9116.6-
Synthesis of phenyl-2,4-hexanedione 148 g (1 mol) of phenyl-2,4-hexanedione was dissolved in ethyl acetate 2
64g, and add 23g of sodium to this at 20-60℃.
g was added slowly. After further stirring and flowing for 2 hours,
After cooling, water 11 was poured into the mixture, concentrated hydrochloric acid was then added dropwise to neutralize the mixture, and the mixture was allowed to stand and the liquids were separated to separate the ethyl acetate layer. The ethyl acetate layer was washed with water and then smoked with anhydrous Mg5O for 92 hours. The desiccant was removed and the solvent was distilled off to obtain 171 g of a dark red oil. The residual oil was then obtained by vacuum evaporation.

Example 13. 6-(4-chlorosulfonylphenyl)
-3-Diazo-2,4-hexanedione (general formula % formula %
) 29.0 g (0.15 mol) of 6-phenyl-2,4-hexanedione obtained in Reference Example 6 was added to 300 g of methylene chloride.
rM! 12.8 g (0.15 mol) of piperidine was added. 31.2 g (0.16 mol) of p-1 luenesulfonyl azide obtained in Reference Example 1 was added dropwise at 10 to 5°C, and the mixture was further reacted at the same temperature for 1 hour. The reaction solution was washed with a dilute aqueous caustic potash solution, washed with water, and dried with anhydrous M) gsO. After removing the desiccant, the solvent was distilled off to form a dark red oil.
8 g was obtained, and the remaining 1N oil was separated by column [silica gel: Fuco-gel C-200, eluent 20-hexane/
Acetic acid fJv = IO/l (V/V)) L, 3-diazo-6-phenyl-2,1-hexanedione 27.0
g was obtained as an orange-red viscous oil. After cooling, the amount of rice crystallized was 17. mρ, 30.0-32.0°C.

HNMRδppm ((:DCll): 2.47(3
H,s,Ctl,), 3.10(411,s,-4:
jjl-C! L2-), 7.28 (5N, s, aromatic ring).

If((Neat,): 2100cm”(-N7
), 1650c+n-' (1:=0).

(216-(4-chlorosulfonylphenyl)-3-diazo-2,4-l\3 obtained in synthesis of xanedione [1)
-Diazo-6-phenyl-2,4-hexanedione IO
, I1g (50 mmol) in chloroform: l5ml
! Chlorsulfonic acid: (5 g
was dripped. After stirring at -5 to 0°C for 2 hours, the mixture was poured into ice water IIl, extracted with chloroform, and the separated chloroform layer was washed with water and dried over anhydrous MgSO4.

After removing the desiccant, the solvent was distilled off, and the remaining 4g of orange oil was added to the column! (Silica gel: Wakogel C-200, solution solution: n-hexane/ethyl acetate = 5/I (V/V)) and 6-(4-chlorosulfonylphenyl)-3-diazo-2,4-hexanedione Obtained 3.0 g as a yellow viscous oil. The ice crystals crystallized after cooling. , mp, 58
．． 0-59.5°C.

'HNMRδppm (CDCl2): 2.40 (
3H,s, -611,), 3.20(4tl,s
, -(:tl, -OH, -CO-) , 7.32 (
211, dd, J-8Hz, phenyLl;
2. C61,7,97 (211,dd, J-811Z,
phen/L-C3, (:5).

IR (Neat): 2130cm-'(-N2),
1660c+n-' (C-0).

Elemental analysis value (C+2tl++ to lN2O, +S) Theory and ethics value: C tree, 45.65, 8 tree, 3.51; N!
, 8.87°Actual value: C! To, 45.59;
H! li, 3.79; N96, 8.68°actual h't+
Example 14. 4-(4-cyaso3.5-dioxohexyl)benzenesulfonic acid (-a formula [I[[]% formula%) 6-(4-chlorosulfonylphenyl)- obtained in Example 13 (2) 3-Diazo-2,4-hexanedione 2.
0 g (fi, 4 mmolf to 15 m acetonitrile
! ! and ifA in 45 ml of water and heated at 30-35°C for 2 hours.
The reaction was stirred for hours. After the reaction, dilute with 40 d of methylene chloride.
After washing twice, the aqueous layer was concentrated under reduced pressure and 4-(4-diazo-3,5-
1.4 g of dioxohexyl)benzenesulfonic acid were obtained as a pale yellow viscous oil.

'lINMrl δppm(CDCl2-DMSO-
d6): 2.37 (311, s.

-(:IIJ, 2.88(211,L,J□7)1z
, -Gmu-(:O-), :1. (17(2H, tJ=7
Hz, -1; II, -C:N2-1-), 7
．． 2] (2H, d, , I=8.511z.

phenyl-C:3. C5), 7.58 (2H, d,
J・8.511z, phen, yl-G2C6),
10.53(III, bS, -3O311>.

It((Neat): 337Qcm-'(Kano), 2120cm-'(-C:N2).

1630cm-' ((:=0).

UV (113cN) λmax (ε): 226
．． 4Hm (28B30).

Elemental analysis value (G+zll+2N205S) theoretical value: C
! To, 48.64; H! t, 4. υ8; N'*
, 9.45°Actual measurement value: C*, 48.75, N9
6,4.11, N%, 9.29° Example 15. 4
-(4-diazo-3,5-dioxohexyl)benzenesulfonate ammonium (general formula [ffl],
Ra=-C113, Y=-50? FH4, m'・2
) 890 mg (3.0 mmol) of 4-(4=diazo-3,5-dioxohexyl)benzenesulfonic acid obtained in Example 14 was mixed with 5-acetonitrile and 28% aqueous ammonia (3-3).
The mixture was stirred and reacted at 5 to 10° C. for 2 hours.

After the reaction, it was concentrated under reduced pressure and the residue was crystallized from acetonitrile, taken off, washed and dried to give 4-(4-siacy:(,5
-Dioxohexyl)benzenesulfonate ammonium 750B was obtained as a white powder.

mp, old °C (dec,).

'HNMRδppm (CDCl2-DMSO-d6)
: 2.40 (3fl, s, -GO-(:lb+),
2.9:t(2H,t,J-8tlz,-C112
-(:0-), 3.06(2H,t.

J=8Hz, -Cll, -C12-CO-), 3.3
4 (4H, bs, -fffil,), 7.20 (2
11,d, J=811z, phenyl-C3,Cs
), 7.70 (211, d,, J'811z.

phenyl-C2, C6).

IR (in Brim): 3430cm-' (FtlJ
, 2120 cm-'(-CN2).

1640 cr' (C knee 0).

UV (II201 person max (ε) + 225
．． 0t++n (22890).

Elemental analysis value (L1211+r, N, 0iS) theoretical value:
(Ni, 4fi, 00; H!t, 4.83: N tree,
13.4+.

Actual value: C%, 45.72; HJ5.09;
N wood, 13.30° Example IS, triethylammonium 4-+4-siacy3,5-dioxohexyl)benzenesulfonate (in general formula [111], 11
”=-CHI, Y=-5O?f?'H4((:2
H! , ) 3. Synthesis of In'・2) 4-(4-diazo-3,5-dioxohexyl)benzenesulfone 11890B (3.0 mmol) obtained in Example t4 was dissolved in 5 ml of acetonitrile and 3 ml of triethylamine.
The reaction was stirred at 10° C. for 2 hours. After the reaction, the residue was concentrated under reduced pressure and washed several times with ethyl ether, and then dried under reduced pressure to give 4
700 mg of triethylammonium -(4-diazo-3,5-dioxohexyl)benzenesulfonate was obtained as a slightly yellow viscous oil.

I N M R δppm (1:D[l:l 3):
1.36 (9fl, t, J=711z, N-C
H2-ell, X3), 2.42 (311, S, -G
o(:11.), 2.96-3.0ti(・IH.

m, -Cl12-Cji2-), 3.16 (6t
l, q, J・7Hz, N-Cji,, -GH,,,x
3), 7.24 (211, d, J=8tlz,
phenyl-C3, C5), 7.81 (2tl.

d, J-811z, phenyl-C2, (6).

IR (Neat): 34JOcm-' (fRI),
2120c+n-' (-N2).

1650cm-' (C・0).

UV(CI+3(:N) λmax (ε):
226.4Hm (23390).

Elemental analysis value (C+J127N3(L;S) theoretical value: C
%, 54.39: H*, 6.85; N%, 1
0.57° Actual value: C tree, 54.11, 8! Ii,
7. +4. N! Ii, +0.36° Example 17. 4
-(4-Diazo-3,5-dioxohexyl)pensene methyl sulfonate (-In the formula [[11], 118=
-CN5. Y=-3O3CH1.

6-(4-chlorosulfonylphenyl)-3-diazo-2,4-hexanedione obtained in Synthesis Example 13 (2) with m'=21 2.
0 g (6.4 mmol) to triethylamine 1.51
nI! , methanol 2.5d and chloroporm 1Orn
The mixture was stirred and reacted at 10 to 15° C. for 6 hours.

After the reaction solution was injected into a human body, it was extracted with chloroform, and the separated chloroform layer was washed with water and dried with anhydrous MgSO4. After removing the desiccant, the solvent is distilled off and the residue is converted into column molecules! I [
Silica gel: Wakokel C-=200° Dissolved solution: Diluted with chloroform to obtain 7:10 mg of ethyl 4-(4-diazo-3,5-dioxohexyl)benzenesulfonate as a pale yellow viscous oil.

'HNMIt δppm (CDCl2): 2.4
2(3fl, s, Gll,), 3.1) 3~. '
1. l8 (411, m, -CJ-Clh-), 3.7
6(:)H,s,-3O3GH,,).

7.4', I(211,d, J-8,5Hz, ph
enyl-C3,G,), 7.83 (2H.

d, J=8.511z, phenyl-C2, C6).

lit (Neat): 2100cm (-(:
N2), 1650 cm-' (c-o).

UV (C1hl:N) λmax (ε): 227
．． 8Hm (30220).

Elemental analysis value ((:+311+4Nt(J,S) theoretical value:
C%, 50.32; H%, 4.55, N%
, 9.0:l.

Actual values: C%, 50.25, H%, 4.61
, N96, 8.97° Example 18. Ethyl 4-(4-diazo-3,5-dioxohexyl)benzenesulfonate (-in the formula [I11], R8・-CI+3
．． Synthesis of Y-5O3C2115゜m'.2) 6-(4-Chlorsulfonylphenyl)-3-diazo-2,4-hexanedione obtained in Example 13 (2) 2.
0 g (6.4 mmol) of triethylamine 1.5
The mixture was mixed in 10 ml of ethanol, and stirred and reacted at 20 to 25° C. for 16 hours. The reaction solution was poured into water, extracted with chloroform, and the separated chloroform layer was washed with water, dried, and the solvent was distilled off. The residual liquid was separated by column [silica gel: Fuco-gel C-200, heel solution: chloroform], and 4-
550 mg of ethyl (4-diazo-3,5-dioxohexyl)benzenesulfonate was obtained as a pale yellow viscous oil.

'iNMRδppm (CDCl2): 1.31 (3
H, L, J=711Z, 5O3CII2C1l, ),
2.42 (311,s, -COO added), 3.04~3
．． 17(4)1. m, -(:II.

(:II, GO-), 4.11 (2H, q, J-7
11z, 5036H2CH3), 7.42(2tl
, d, J□8.5Hz, phenyl-C: 3.
G, ), 7.82 (2H, d.

, I=8.5Hz, phenyl-C2, C6).

lit (Neat): 212 (JCm-'(-C
N2), 1645cn+-' (C-0).

UV (111, [;N)λmax (ε): 2
29. Onm (28930).

Elemental analysis value (CI 41116N205s) theoretical value:
C96,5+, 84; H%, 4.97. N*,
8.64° Actual value: C%i, 51.77; H! 4.85; N! 8.73゜actual hζExample 19. 6
-(4-Aminosulfonylphenyl)-3-thiaso2
．． 4-hexanedione (in the general formula [IO], l+8
=-CH3,Y=-502Nl12. 6-(4-chlorosulfonylphenyl)-3-diazo-2,4-hexanedione Ig obtained in (2) of Example 13
(3.2 mmol) was dissolved in acetonitrile (5 ml), 2 g of 28% aqueous ammonia was added dropwise at 5-10'C, and the mixture was further stirred and reacted at room temperature for 6 hours.

After the reaction, it was concentrated under reduced pressure and the residue 7 was separated by column [silica gel:
Fuco-gel C-200, solution; n-hexane/ethyl acetate = 5/] -+2/l (V/V)]
4-Aminosulfonylphenyl)-3-diazo-2,4
-Hexanedione 800B was obtained as white crystals.

mp, +09.5-111.5°C.

'IINM+(δppm(CDCI+-DMSO-d6
): 2.41 (3H, s.

[:0 to 11. , ) , :1.02~3.11(41
1,m,-ell,l;II,-), 6.42(2)
1゜bs, -Nlh), 7.35 (21Ld, J□
8Hz, phcnyl 2. C6).

? , B3 (211, d, J-8Hz, phenyl-1
;+, (:5).

111 (Kllrj2): 2120cm-'(-C
N2), 1625 cm-' (C-0).

UV (C113CN) λmax (ε): 2
28.8r+m (29820).

Elemental analysis value (1; 121113N304s) Theoretical value:
C! To, 48.80; H*, 4.44; N!
li, 14.2:I.

Actual value: C*, 48.69; H! Ii, 4.3
9; N*, 14.4+.

Example 20. 6-(4-N,N-ethylaminosulfonylphenyl)-3-diazo-2,4-hexanedione (in the general formula [IU], 1lI=-C11,, Y
=-502N (C21+,)2. Synthesis example of [11'-2)! 1 g (3.2 mmol) of 6-(4-chlorosulfonylphenyl)-3-diazo-2,4-hexanedione obtained in 3-(2) was dissolved in 5 ml of acetonitrile, and 0.6 g of diethylamine was dissolved in this. The mixture was added dropwise at 5 to 10°C, and the reaction and post-treatment were carried out in the same manner as in Example 19 to obtain a crude oil. Column division E silica gel: Wako gel C-200, eluent: n-A
xane/ethyl acetate-5/I-+2/I (V/V)]
L/, 6-(4-N,N-diethylaminosulfonylphenyl)-3-diazo-2,4= hexanedione 7
70 mg was obtained as a slightly yellow viscous oil.

'IINMRδppm(CD(:I3): 1.1:
I(6N, t, J-711z, N-(:It2Cli
X2), 2.42 (311,s, GOCI,), 3
．． 00-3.15 (411, m.

-CIIzGIIzC (1), 3, 23 (41
1, q, J=711z, N-(:IbCH*
X2).

7, :15(211,d, J=8.511z, ph
enyl-(:+,C,,), 7.72(28d, J
□8.5tlz, phenyl-G, , C6).

III (Neat): 2110cl'(-CN
2), 1640 cm-'([;=0).

UV([;H,l;N) λll1ax(ε):
232.5nrn (18950).

Elemental analysis value (C, 611□1N304s) Theoretical value: C
%, 54.69, H! 11, 6.02. N*,
11.96° Actual value: C! II;, 54.6Q,
H! 5.86. N! 12.11゜Example 21
．． 6-(4-morpholinosulfonylphenyl)-3-
Diazo-2,4-hexanedione (general formula [IIr] 1
．． : where R8= -co, y=real/iei 6-(4-chlorosulfonylphenyl)- obtained in Example 13 (2)
3-Diazo-2,4-hexanedione Ig (: 1.2 mmol) was dissolved in 5 ml of acetonitrile, and 0.83 g of morpholine was added dropwise to this at 5 to IO''C, followed by the same procedure as in Example 19. The reaction and post-treatment were performed to obtain a crude oil.This was used for the column! [Silica gel: Wako gel c-
200. Melting a: n-hexane/ethyl acetate 5/1→
2/l (V/V)] 800 mg of L,b-(4-morpholinosulfonylphenyl)-3-diazo-2,4-hexanedione was obtained as a pale yellow viscous oil.

') INMI(δppm(II:DCI3): 2.
42 (3fl, s, COCl*), 2.99 (4H,
t, J-511z, morpholine-
C2, [;2□, C6, C6□), 3.04~:
+, l6 (411, m, -cl12c112co-),
3.74 (48,t,, J=5Hz.

morpholine-C3,C3',G,,,C9・
), 7.4:I(2f1.d, J=8Hz.

phenyl-C3, (:5), 7.67 (211
, d, J=8Hz, pt+enyl-C2°G6).

IR(Neat): 2130cm-'(-CN2)
, 1645 cm-' (11 knee 0).

IJV(C113(:N) λmax (ε):
230.9nn (29350).

Elemental analysis value (C+c, tl+J30qs) Theoretical value: C
Book, 52.59; H! %, 5.24; NJl
l, 50° Actual value: C'4, 52.42;
H')i, 5.30; N! In, Il, 61i.

Actual h'tz example 22. 6-(4-piperidinosulfonylphenyl)-3-diazo-2,4-hexanedione (general formula [II[]i,: 11'= -C:113.
Synthesis of Y=-5O20, m'・2) 6-(4-Chlorosulfonylphenyl Ig (3.2 mmol) obtained in (2) of Example 13 was dissolved in acetonitrile 5d, and piperidine 0 .65g was dropped at 5~IO℃,
Thereafter, the reaction and post-treatment were carried out in the same manner as in Example 19,
A crude oil was obtained. This was separated by column [silica gel: Fuco-gel C-200, eluent: n-hexane/ethyl acetate 5/1 → 2/I (V/V)] t,, t(4-piperidinosulfonylphenyl) 730 mg of -3-cyaso-2,4-hexanedione was obtained as a pale yellow viscous oil.

'IINMI(δppl!l(CDI;13):
1.37 ~ 1.51 (211, +++, piper
idine-4,C.・), 1.60 ~ 1.74
(4H, rn, piperidine-c,,c
,-,[;5,c i), 2.42(311,s,CO
G) 13), 2.96 ~ 3.18 (811, m, -
CHlf;H, GO- and piperidine-C2
J:2□,C6,C6□)7, :18(211, d
, J.811z, pt+enyl-G3. C5),
7.67 (2tl, d.

J=811z, phenyl-1;2. cli), II
(Neat): 2130cm-'(-CN2),
1640 cm-' (G=0).

UV (ell, ON) λmax (ε): 23
1.2 nm(29]-1Q).

Elemental analysis value (CI71121N304S) Theoretical value: C
q6,5[i, I8, H! lli, 5.82. N
Main, 11.56° Actual value: C tree, 56. Old: 8%,
ti, IO; N zero, 11.49° Reference example 7. Synthesis of 9-phenyl-2,4-nonanedione (1) Synthesis of 4-phenylbutanol Lithium aluminum hydride 67 in 2.5 I of tetrahydrofuran under a nitrogen stream A tetrahydrofuran solution containing 225 g (1.37 mol) of 4-phenylbutyric acid dissolved therein was added dropwise at 15 to 25° C., and the reaction was further stirred at room temperature for 1 hour. After the reaction, the mixture was poured into 31 g of ice water and 200 g of sulfuric acid, and then extracted with ethyl acetate.

The ethyl acetate layer was treated with anhydrous M, qSO,.

After drying, the solvent was distilled off, and 227 g of the residue was distilled under reduced pressure.
191 g of 4-phenylbutanol of the 113-+15 DEG C. 10.5 mmH3 fraction was obtained as a colorless oil.

(2) Synthesis of 1-chloro-4-phenylbutane 300 g of thionyl chloride was added dropwise to 189 g (1,26 mol) of 4-phenylbutanol obtained in (1) at room temperature, and then
The reaction was stirred and refluxed for an hour. After concentrating the reaction solution, the residue was distilled under reduced pressure to obtain 149 g of 1-chloro-4-phenylbutane in a bp, 122-123° C./17 mmHg fraction as a colorless oil.

(Synthesis of 3j9-phenyl-2,4-nonanedione) 10.7 g of 60% sodium hydride (oil-based) was suspended in 140 rnI of cyclohexane under a nitrogen stream, and 26.71 g of 2,4-pentanedione was added to this with stirring. < (0,2
A cyclohexane solution of 67 mol) was added dropwise at room temperature, and the reaction was further stirred for 2 hours. Furthermore, 34.1 g of N,N,N',N'-tetramethylethylenediamine was then added to 185 ml of n-butyllithium (1,6M n-hexane solution).
After adding dropwise at ℃ and stirring for 2 hours at room temperature, (2) was obtained!
52.3 g (1 mole of OJ) of -chloro-4-phenylbutane was chopped, and the mixture was stirred and reacted at room temperature for 3 hours. The reaction solution was poured into ice water IO, neutralized with dilute hydrochloric acid, and then extracted with ethyl acetate. After washing the separated ethyl acetate layer with water, anhydrous M
It was dried with g5O. After removing the desiccant, the solvent was distilled off and the remaining fh was separated on a column [Silica gel: Fuco-gel C-200]
, Eluent: Benzene/Rohexane=4/I (V/V
)] L, 9 7 en) Li-2,4-/chindione 8
．． 5g was obtained as a pale yellow oil.

'INMRδppm(f:Dfl:I,): 1.3
4 to 1.71 (6! I, m, -cJCll, ell, -
GlhGO-), 2.04 (311,S, GOCll
a), 2.26 (211°, J-8tlZ, -Cl1
2CHa-COOdan1-), 2.61 (211
, L, J=8Hz.

Ar-C12-J, 3.55 (2fl, s, -GOG
82GO-: Keto type]/7).

5.47 (eyes, s, -1; -f; H-GO-: enol type 6/7), 7.16 ~7, :lo (5
H, +n, aromatic ring), 15.49 (Ill, bs, OH
(Eng. l-le)).

IR (Neat): 1725cm-', 1
600cm-Example 23. 9-(4-chlorosulfonylphenyl)-3-cyacy2,4-nonanedione (in the general formula [[11], l18= -C11,, Y
=-3O2CJ/.

Synthesis of m″・5) (1) 7.1 i g (0,034 mol) of 3-diazo-9-phenyl-2,4-nonanedio was dissolved in methylene chloride 25
After adding 3.4 g (0,034 mol) of triethylamine, 6.7 g (0,034 mol) of ρ-toluenesulfonyl azide obtained in Reference Example 1 was added dropwise at 0 to 5°C. The reaction was carried out at 7M degrees for 1 hour. The reaction solution was washed with a dilute aqueous caustic potash solution, then water, and dried over anhydrous MgSO4. After removing the desiccant, the solvent was distilled off to form a dark red oily substance.
2g was obtained. Next, remove the residual oil from the column! [Silica gel: Fuco-gel C-200, eluent: n-hexane/methylene chloride 2/1 → 1/1 → 1/4 (V/V)]
5.2 g of 3-diazo-9-phenyl-2,4-nonanedione were obtained as a yellow viscous oil.

'IINM+(δpp+n(CDCIs): 1.3
5-1.74 (611,m, -C:muc11.cli
[:112co-), 2.4a(:+11.s, co
c+1), 2.61 (211,j.

, J=811z, Ar-CH,-), 2.70(2
11, tl=8tlz, -C1lzf:0-).

7.15-7. :to(511,m, Ho Xiangkan), 11
t (Neat): 2100cm-'(-CN2)
, 1650 cm-' ([:=0).

+219- (4-chlorosulfonylphenyl)-3-
Synthesis of cyaso-2,4-nonanedione 3.6 [(14 mmol) of 3-diazo-9-phenyl-2,4-nonanedione obtained in fil was dissolved in chloroform 1
Chlorsulfonic acid 6.5% dissolved in 0ml at -5~0℃
g was added dropwise. Did you stir the reaction at the same temperature for 2 hours? The separated chloroform layer was washed with water and dried over anhydrous MgSO4. After removing the desiccant, the solvent is distilled off, leaving an orange oily residue! , 7g was separated by column [silica gel: Fuco-Kel C-200, eluent: n-''\xane/ethyl acetate = 5
/l (V/V month, 9-(4-chlorosulfonylphenyl)-3-diazo-2,4-nonanedione 1.4 g
was obtained as a pale yellow viscous oil.

'IINMRδppm (CDCI*): 1.37~
1.75 (6H, m, -Cji.

Cjj, CJi:H, CD-), 2.43 (:dan, s,
GO (:lb), 2.74 (411, m.

co, co-) 1bi8 r-elf, -), 7.41
f2tl, d, J□811z, p)+enyl-C2,
Cg), 7.95 (2tl, d, J.
811z, pl+envl-+3. (:,).

IR (Neat,): 2100cm-'(-(:N
2), 1645cl'((:=O).

UV (CI13f;N) λmax (ε)
: 242.2Hm (18680).

Elemental analysis value (G+5H+7αN,,04S) Theoretical value: C
Zero, 50.49; H! To, 4.80. N'X,
7.85°Actual measurement: CL50.6:l; H'!
,4. ii9; N*, 7.77° real/ih Example 24.
9-(4-chlorosulfonylphenyl)-3-cyaso2.4 dinonanedione obtained from ethyl 4-(7-cyaso(j,8-dioxononyl)benzenesulfonate (general formula % formula % Example 23-12) 1.1
g N, 1 mmol) to triethylamine 0.7-
After mixing with 7.3 d of ethanol and 7.3 d of ethanol, reaction and post-treatment were carried out in the same manner as in Example 18, and the crude oil was
:? Ta. This was separated by column [silica gel: Wakokel C]
-200, elution i: Elution with chloroform gave ethyl 4-(7-diazo-6,8-dioxononyl)pensenesulfonate 850B as a pale yellow viscous oil.

' HN M 11 δppm ((:DCI3):
1.23-1.34 (5t(, m, -CH.

CH2(:II□l; O- and -3tl, C112C1
11), 1.59-1. ii4 (411, m.

Ar-[:112cjjl- and -CJ(:N2(:0
-), 2.36 (311,s, -[111).

2.60-2.69 (411,m, Ar-C11,- and -CH,GO-), 4.04 (211,q, J-71
12,-5Q,,C1l,I:l-1,), 7.27
(2H,d,,I=8.511z.

phcn, yl-C2, C6), 7.73 (211,
d, ,I=8Hz, phenyla, ,C5),.

III fNeat, ): 2100c
m-'(-(:N2), 1640 cm-'(C=0).

Elemental analysis value ([;+ 71122N20ss) buried 1fj
f4 ko C*, 55.72, H! I...
6.05; N! To, 7.64.

Actual value: C'li, 55.61, 8'li, ii
, 2! : N, 7.881 Reference example 8. Synthesis of 1-phenyl-3,5-octanedione 4-phenyl-2-butanone 46.8 g (0,,31
mol) and ethyl butyrate (1,95 mol) were mixed in toluene + 20 rnl and heated at 20-60°C.
Then 7.3 g of sodium was slowly added. After further reacting with stirring for 9 hours, the reactor was heated overnight. Next, 300 rn of water and 45 rn of concentrated hydrochloric acid! ! Pour the reaction solution into the tank and neutralize it.
After extraction with ethyl acetate, the organic layer was separated, washed with water, and anhydrous Mg
Dry with 5U4. The desiccant was separated, the solvent was distilled off, and 84 g of the red-orange oily substance remaining was distilled under reduced pressure to obtain 15.4 g of BP, 166-B tandione as an RA R-colored oily substance.
゜'HNMRδppm ((:DCI 3): 0
．． 9:l(:)II,t,J-7)1z,-Cfl,,
).

1.53-1.67 (211, m, -1; II, f; I
I3), 2.23(2+1.j,, I=7112°-[:jjx(:l12cl+,,), 2,6
Of2H, L, J = 711z, Ar-(, l
l2Ll11(:0-).

2.94 (211,L, J=711z, Ar-G
11. -), 3.52 (2H,s, - to Ocu,c
o-: Keto type 3/10), 5.45 (IILs,
-C=Cjj-GO-: enol type 7/10), '7
．． 16-7.211 (511, m, aromatic ring) 15.46
(III, bs, 01l(xnor)).

lit (Nealj: 1B00cm-Example 25.1-+4-chlorosulfonylphenyl)-1
-Diazo-3,5-octanedione (general formula rI [1]
In, R8・CIl, Cll2c11□-1Y=-5
Synthesis of O□α, m'=2) (1) 4-siacy 1-
Synthesis of phenyl-3,5-octanedione 7.6 g of l-phenyl-3,5-octanedione obtained in Reference Example 8 (J5 mmol was mixed with 70 mff of methylene chloride)
After adding 3.0 g (35 mmol) of piperidine, 7.42 g (38.3 mmol) of p-toluenesulfonyl azide, which was diluted with jtI in Reference Example 1, was added dropwise at 0 to 5°C. The reaction and post-treatment were carried out in the same manner as in Example 12 (1), yielding 12 crude oils. This was published as a column [Silica gel: Fuco-gel C-200, eluent:
n-hexane/methylene chloride・5/1→3/1→+7+
(v/V) ]4-diazo1-phenyl3
, 5.3 g of octanedione were obtained as a yellow oil.

11NMII δI) pil (1; DCI3):
0.97 (:])I,t,,J-7)1z,(:II
,,).

1.6:1~1.77(211,m,-(:+12CI
+3), 2.68 (21+, t, J=711z.

-CjjlGII□(:II,), 2.414 ~
3.11 (411, m, hell, Ishishi).

7.19-7.3: J (5tl, m, aromatic ring).

III (Neat,): 2140cm-'(
-CN2), 1650c+n-' (G-0).

(2) 1-(4-chlorosulfonylphenyl)-4
-4-Diazo-1-phenyl-3,5-octanedione 5 obtained in synthesis (1) of diazo-3,5-octanedione
．． 15 g of chlorosulfonic acid was added dropwise at -10 to -5°C to a chloroform solution in which 2 g (21,: l mmol) was dissolved, and the reaction and post-treatment were carried out in the same manner as in Example 12 (2). 3 g of a crude oil was obtained. This was separated by column [silica gel: Wakogel C-200, eluent: n
-hexane/ethyl acetate 5/1-+: l/I (v/V
)] L, 1-(4-chlorosulfonylphenyl)-
900+ ng of 4-cyaso 3,5-octanedione were obtained as a pale yellow viscous oil.

11NMII δppm (f; HCH3): 0.
98 (:lH,t,,I=7Hz,C:111).

1.63-1.77 (211, m, -diHCH3),
2.63 (211,t, J=711z.

-(:ll2C:f12GII3), 3.09 (2
11,t, J-711z, Ar-G11. ,GH-)
.

3.22 (2H,t,J・711z,Ar-C8,-)
, 7.49 (2tl, d, J-9Hz.

phcnyl-C2, C6), 7.95 (2)1
, d, J=9Hz, phenyl-C3,C5)
.

III (Near): 2140cm-'
(-CN2), 1650cm-' (G-07゜Elemental analysis value (C: +Jl+r, αN20.S) Theoretical value: C'4
i, 49. +15, H! %i, 4.41; Nk
, 11. +7゜actual d (value 20, 48.8!I,
H! , 4.66; Nk, 8.34° Reference example 9.
13-7enyl-2.4-) Synthesis of lysocandione fi + Synthesis of monomethyl sebacate chloride 432.6 g (2 moles) of monomethyl sebacate 360 g of dithionyl chloride was added dropwise at 60°C, and the reaction was carried out under stirring under reflux for 2 hours. The crude oil obtained by concentrating the reaction solution was distilled under reduced pressure to obtain 400 g of sebacate monomethyl chloride in a 11 g fraction (bp, 145-150° C./4 + nm) as a colorless oil.

(2) Synthesis of methyl 9-benzoylnonanoate (sebacic acid monomethyl chloride 213 obtained in 11, fig.
(0.91 mol) was dissolved in benzene 900d and 5℃
From then on, 153 g of aluminum chloride was gradually added. Next, after carrying out a stirring reaction for 1 hour, the reaction solution was poured into 1f of ice water.
fi, and the benzene layer was separated. The organic layer was washed with water (500 m7!
a25O4), the solvent was distilled off, and the residual red-orange oil +2
00g) in column fraction Ill [Silica gel: Fuco-Kel C
-200, eluent: n-hexane/ethyl acetate-4/]
(V/V)] to obtain 738 g of methyl 9-hensoylnonanoate as a colorless viscous oil. Note that the ice crystals were crystallized after cooling. mp, 37.0-38.0°C.

'HNMRδppm (CDC11) River, 26-1.40
(811, m, -Ljjz-x4), ! , 59-1.
75 (4)1. Ill, -C(H:1hcllz- and -CCH2(:0OCII:+), 2.30(2
11,t,J・7.3Hz,-CI,[':0OCII
,).

2.9fi (2H, t, J=7.3Hz, Ar-GO
Ctl, -), 3.67 (:lIl, s, - to UUG
IL! l, 7.42-7.58 (:III, m, p
henyl-G3. (:4.C5).

7.96 (211, d, J-7, 3tlz, pt+
eny l-C,, Cal.

It((KBr37): 2900c+n-', 2
850cm-', 1740cm-'(COOI':
II3), 1680 cm-' (C・0).

(18.3 g of methyl 9-benzoylnonanoate obtained in synthesis (2) of 3110-phenyldecanoic acid
(66 mmol) diethylene glycol IQOmt'
1.6 g of 80% hydrazine hydrate I was dissolved in
The mixture was converted to Pfi with dilute hydrochloric acid and extracted with ethyl acetate.

The organic layer was washed with water, dried (anhydrous Mg5O, etc.), the solvent was distilled off, and the residue was recrystallized from ligroin to obtain 14.5 g of IO-phenyldecanoic acid as white flaky crystals. mp, I! 4
．． 5-46.5°C.

11NMRδppm (GDC: 13): 1.24~
1.31 (IflH, +++, -GH,, -X 10)
, 1.58-1. li3 (411, m, Ar-Cl
12Gjl- and -c6f:+12(:0011),
2, 34 +211, t, J=7.311z
, -Cll,f:0011) ,2,80(21
1, t, J=7.7flz, Ar-fl:It, -),
7.14-7.19 1111. m.

phenyl-C, , G, +, C6), 7.2f
i~7.34 (211, [Il, pl+enyl[+3
．． [;5).

IR (KBr12): 1670 cm-' (C=0).

(13.7 g (55 mmol) of 10-phenyldecanoic acid obtained in synthesis (3) of methyl 4110-phenyldecanoate was dissolved in chloride, methylene IOOrnt!,
13.1 g of thionyl chloride was added dropwise at ℃ and stirred for 1 hour.
It reacted smoothly. After concentrating the reaction solution, the residue was diluted with methanol 2
(20°C or higher) in 0ml and 11.2g of triethylamine)
The mixture was added dropwise at 20±5° C. and reacted with stirring for 1 hour. The reaction solution was poured into 10 W of water, extracted with methylene chloride, and the organic layer was washed with water (100 ml x 3) and dried (anhydrous Mg5O
:+), the solvent was distilled off. The residue (15.4 g) was separated by column [silica gel: Fuco-gel C-200, eluent: methylene chloride, methyl 10-phenyldecanoate 101 g]
was obtained as a tan-colored oil.

1.11NMRδppm (CDC13): 1.24
~1.32 (1011, m, -GJ-x 5), I
, 56-1.61 (4H, m, Ar-Cf12C
Mu-and-elf.

1hc00-), 2.29 (211,t, J=7.3
11z, -Gjj, C00-), 2.59 (2H, t
, J=7.311z, Ar-C11-), 7.16~
7.18 (311, n+.

phenyl-G, C4, C, ), 7.24-7.
30 (2H, [Il, phenyl-C*.

C6).

Ill (Neat,): 1720cm” (G=0
).

(5) 9.2 g of methyl 10-phenyldecanoate obtained in synthesis (4) of 13-phenyl-2,4-tridecanedione (
Add 35 mmol) and 2.4 g (42 mmol) of acetone, and add sodium 268+ at 10 to 40°C.
ng (11.7 milliatoms) was slowly added, and the reaction and post-treatment were carried out in the same manner as in Reference Example 5.
．． 8g was obtained. Column molecule l [silica gel: Fuco-gel C-200, eluent: n-hexane/ethyl acetate = +o/l (V/V) IL, lj-7s-nyl-2,
1.2 g of 4t.lysocandione was obtained as a yellow oil.

'IINMII δppm (LDCI:+):1.
29 (10tl, bs, -Cjjz-x 5).

I, 59 (411, bs, Ar-(, It21'
4- and -1,:Il, e1+2fl:0fl12-)
2.05 (3tl,s,-coall,),2.
26 (211,t,J-)i,511z,-co
c.

al12coc)l:+), 2. ao (2tl, t
, J=7.211z, Ar-6%-J, 3.56(2
11,s, -GOC 肚CO-: Keto type 3/10),
5.48 (III, s.

-[knee+llf; 0-: enol type 7/10),
7.14-719 (: Jll, m.

2. to phenyi. C4, C6), 7.25-7.3
0(211,m, phenyl-(:,,,C,,)
, 15.51 (Ill, s, Q (esor)).

IR(Neatl: 1600cm-'((knee 0)
.

Example 26.1: I-(4-chlorosulfonylphenyl)-3-diazo-2,4-tridecanedione (in the general formula [[], R8= -ell,, Y=-5O2
cfL, m' = 9) (7) Synthesis (Synthesis of 113-diazo-13-phenyl-2,4-tridecanedione) I3-phenyl-2,4-tridecanedione obtained in (5) of Reference Example 9 Dissolve 1.1 g (4 mmol) of ion in 10 ml of methylene chloride, and dissolve 0.33 g (4,0 mmol) of piperidine in 10 ml of methylene chloride.
He who added mmol) is a reference example! p-Toluenesulfonyl azide 850B (4.4 milliliters) obtained in
The mixture was added dropwise at 100° C., and the reaction and post-treatment were carried out in the same manner as in Example 12 (1) to obtain 1.1 g of a crude oil. The solids were separated by column separation [silica gel; Wakokel C-200°; eluent: methylene chloride] to obtain 1.0 g of 3-siacy 13-phenyl-2,4-tridecanedione as a viscous oil at °C.

Note that the ice crystals were crystallized after cooling.

+np, 29.0-31.0℃0 HN M It δppm (LDCI3): 1.2
9 (1011, bs, -C1l, -x 5).

1.59~l, 6'l (411,m, Ar<1hG
lh- and -C8,G112co-).

2.44(,itl,s,-GOGII,,),2
．． 59 (211,t,, 1-7.711z, -C1f.

Go-), 2.69 (2tl, (J-7, 5f
lz, Ar-1:lj2-), 7, 16-7,
18(:IH, +n, pt+enyl-G2.C4,5
), 7.24-7.30 (2N, m.

phenyl-f:*, Cs).

II (Neat): 20! JOcm-'(-(:
N2), 1640 cm-' (C=0).

(:Il 13-(4-chlorosulfonylphenyl)
-3-diazo-2,4-tridecanedione (general formula % formula %) 3-diazo-13-phenyl-2,4 1it at +11
-) In a chloroform solution containing 0.88 g (2.8 mmol) of lysocandione, 1.0 g of chlorsulfonic acid is added. :l
Og was added dropwise at =IO to -5°C, and the reaction and post-treatment were carried out in the same manner as in (2) of Example 12 to obtain a crude oil:
6. Separate the stiffness by column [silica gel:
Fuco-gel C-200, melting solution: methylene chloride, l
j(4-chlorosulfonylphenyl)-3-siacy 2
．． 4-tridecanedione 150B was obtained as a pale yellow viscous oil.

Note that the ice crystals were crystallized after cooling.

mp, 48.5-50.0°C.

II NM R690m ((:DGI31:1.30
(lull, bS, -(:II, -X 5).

1.59-1.64 (4N, m, Ar-(:112(l
j, - and - (:JC112GO-).

2.45(',111.s,-[:0CII,,l,
2.68 to 2.75 (4tl, +n, 8"-C and-
GjjlGO-), 7.41 (211, d, J=
6.6Hz, phcnyl-(: 1. at 2°), 7.9
4 l2l1. d, J=6.611z, phen
yl-G3. ).

IRtNeat): 2090cm-'(-CN
2), 1630 cm-' (G=0).

11V (+lL, GN) λmax (ε):
241.3nm (25790).

Elemental analysis value ((:+qlhsαN204S) theoretical value:
0%, 55.26; [,6,10; [,6,7
+1゜Actual value 20 wood, 55.38, H! t, 6. +
7. N! , ti, 69° Reference Example 10. Synthesis of 16-phenyl-2,4-hexadecanedione fi + Synthesis of methyl 10-oxo-13-phenyltridecanoate Nitrogen stream, 300 mt' of ethyl ether and magnesium (shavings) 17.1 g of β bromide with vigorous stirring.
- 140 g (0.7 mol) of phenethyl (ethyl reagent solution) was added to a solution of 150.1 g (0.64 mol) of sebacate monomethyl chloride obtained in Reference Example 6 (1) dissolved in ethyl ether (500 d). It was added dropwise at 50 to -30°C. One culm was brought to room temperature, stirred and reacted at room temperature for 2 hours, and then water was poured at 500 rn! The needle layer obtained by liquid separation was washed with water, dried (anhydrous Mg5O, etc.), and the solvent was distilled off to obtain 203 g of crude oil. Ta. Column fraction of crude oil #
I [Silica gel; Fuco-gel C-200, eluent 20-
Hexane/ethyl acetate 4/I fV/V) ] L,
10-year-old xo-13-phenyltridecanoate methyl 99
．． 7g of colorless oil is IR7.

'IINMRδppm((:DGl+): I, 2
3-1. :10(8H,m,-G%-x41.1.51
~1.70 (411,m,-(:01;H2GH,-
and -cy[;lI2[;00[:lL+), I
, 81N2. Ql(211,m,8r-GI12(:%
-), 2.30(', !II, t, J"7JHz, -C
112(:00Gl13), 2.36-2.4:] (
411, m.

-CIhCOGjl-), 2.5:] ~2.72(2
H, m, Ar-Cjj-), 3.66 (311, S,
-COOCI+3), 7.13-7. :II(511
, m, aromatic ring).

l1l(NCat): 2!150cm-', 28
00cm-', 1730c+n-'((:0UC)
L+), l'710cm-' (C=O).

(2) Synthesis of 13-phenyltridecanoic acid 56.8 g (0,178 mol) of methyl lO-oxo-13-phenyltridecanoate obtained in (1) was dissolved in 600 Tnl of diethylene glycol, and 50 r of 80% hydrazine hydrate was added.
nI! The mixture was acidified with dilute hydrochloric acid and extracted with chloroform. The organic layer was washed with water, dried (anhydrous Mg5O4), the solvent was distilled off, and the residue was recrystallized from ligroin to obtain 44.4 g of 13-phenyltridecanoic acid as white flaky crystals. mρ.

51.5-52.5°C.

'IINMRδppm(DMSO-d,l: 1.2
4-1J3 (16t1.m, -f:1h-X 8),
I, 47-I, 58 (4tl, m, Ar-CH
2Cjj, H- and -Cjjz (1:J GOOfl)
, 2, 18 (211, t, J-7, 3Hz
, -GIIzCOOII).

2.48-2.58 (211,m, Ar-C11,-
), 7.11-7.211 (5N, m.

aromatic ring), 11.89 (III, bs, -0O
H).

111 (KBr tablet): 2900c+n-', 2850
cm-', 1680 cm-' ((knee 0).

(Synthesis of methyl 3113-phenyltridecanoate (2)
22.4 g of 1:1-phenyltridecanoic acid (77
mmol) in methanol 60rnI! and 2.2g of sulfuric acid
The mixture was reacted with stirring under reflux for 1 hour. Concentrate the reaction solution and add 1 part of water.
After injecting 00 Inl, methylene chloride extraction was performed. The organic layer was washed with water, dried (anhydrous Mg5O, ), the solvent was distilled off, and the residue M (33 g) was separated on a column [silica gel: Fuco-gel C
-200, the solution solution was mixed with methylene chloride to obtain 17.6 g of methyl 13-phenyltridecanoate as white crystals.

Ridge 30.5-31.5℃.

+1NMRδppl[lt[:DClt): 1.2
5-1.29 (16tl, m, -CJ-xll),
1.56-1.63 (4)1. m, -C11, CIl
□C00Cf13 and Ar-G11□Gjjz-'l
, 2.30 (2H,t, J-7,511z,-1
;%(:00(:ll+), 2.60(2H,t,
, l=7.8112. 8r-CII2-), 3.66
(3H,s,-GOOCHa)7, lti ~7.21
1 (311, m, phenyl-63, C, , C
,, ), 7.24-7.29 (2H, m, phen
yl-C2, (:e).

11 (KBr) + 2900cm'''', 285
0 cm-', 1730 cm-' (C-0).

i41 Methyl 13-phenyltridecanoate obtained in synthesis (3) of 16-phenyl-2,4-hexadecanedione 15.
9 g (55 mmol) and acetone 3.8 g (66
To this, 420 u+g (18.3 mmol) of sodium was slowly added at 10 to 40°C, and the reaction and post-treatment were carried out in the same manner as in Reference Example 5 to obtain a crude oil. This was separated by column separation [silica gel: Wakogel C-200, elution m: n-hexane/ethyl acetate = 1
0/l (V/V) ] L/, 16-7 Ale-2,
1.8 g of 4-hexadecanedione was obtained as a yellow oil.

'IINMRδppm (CDCl2): 1.29 (+
611. bS, -cll, -xa).

1.56-1. li3 (411,+n, -cll,
co2co- and Ar-G112GHz-).

2.050111. s, 4:OCR,), 2,
26 (21+, t,, J-6,5Hz, -ell,
l:0c)12coalli), 2.60(2N
, L, J・7.2tlz, Ar-Ct12-), 3
．． 55 (2tl, s, -GO (:It, [:0-:keto type 3/10), 5.47 (IH, s, -G=(:H
(:0-: enol type 7/10), 7.14-7.
19(:ill, m.

phenyl-2. (:,,G6), 7.25~7
．． :10(2H,m, phenyl-(:1°C1),
15.51 (l) I, s, -0Ji (enol))
.

Ill (Neat): 1605cm-'(C
=0).

Example 16 27.16-(4-Chlorsulfonylphenyl)-3-diazo-2,4-hexadecanedione (in the general formula [IIr], R'= -(II,, Y=-50
Synthesis of 2C1, m' = 12) (l(3-thiaso1
Synthesis of 6-phenyl-2,4-hexadecanedione 16-phenyl-2,4- obtained in Reference Example IO (4)
1.5 g (4.5 mmol) of hexadecanedione in methylene chloride 1iInI! Dissolved in piperidine 375
After adding B (4.5 mmol), the p obtained in Reference Example 1
-Toluenesulfonyl azide 954mg C4,! l
mmol) was added dropwise at 0 to 5°C, and as follows, Example 1
The reaction and post-treatment were carried out in the same manner as in 2-(1) to obtain a crude oil.

Stiffness column 51 [Silica Kel: Wako Kel C-20]
0, eluent: methylene chloride J, 3-thiaso I6-phenyl-2,4-hexadecanedione I, :l
g as a yellow viscous oil.

II N M It δppm (CDCl2): 1
．． 29 (16H, bs, -Cji-x 8).

1,59~I,6:l (411,m,Ar-
C112Cjjz- and -[:%112[10-]
.

2.44(311,s,-COC肚), 2.59(2
H, t, J・7.511z, -%f;0-), 2.70
(211,t, J=7.511z, Ar-(:If,-
), 7.16-7.18 (:lIl, m, pheny
l-G2. G, +, GJ, 7.24~7.30 (2
11, m.

phcnyl-G, II:J.

IR(Neatl: 209Qcl'(-GN2),
iLtOcm-'(C=O).

(:>l 16-(4-chlorosulfonylphenyl-
3-Thiaso2.4-Hexadecanedione (General formula %Formula %
The mixture was added dropwise at -5°C, and the reaction and post-treatment were carried out in the same manner as in Example 12 (2) to obtain 00+ ng of a crude oil. Column fraction M [Silica gel: Lycium gel C-2]
00, eluent: methylene chloride] to obtain 140 mg of 16-(4-chlorosulfonylphenyl)-3-diav-2.4-hexadecanedione as a pale yellow viscous oil.

'HNMRδppm((:Dfl:I,) :1.30
(1611, bs, -C%-X8).

1.59-1. b:] (4H,!11.Ar-C11
2CII2-1bi-c! L, cH2co-).

2.45 (3)1. s, -0C113), 2
, 68-2.75 (4tl, m, Ar-% and -(:
14. , GO-), 7.41 (2+1, d, J=6
．． 6flz, phenyl-G2G, ;), 7.95
(2H, d, J=6.611z, phenyl-C*
,(:,,).

IR(Neatl: 20!lOcm-'(-GN2
), 1635 cm-'((>O).

Reference example 11.1-cyclohexyl-5-phenyl-1,
Synthesis of 3-pentanedione (1) Preparation of ethyl cyclohexanecarboxylate 75 g (0.51 mol) of cyclohexanecarboxylic acid chloride was added dropwise to 45 g of ethanol, 78 g of triethylamine, and 120 ml of toluene at below 15°C, and the mixture was stirred at room temperature for 3-pentanedione. The reaction was stirred for hours. Pour the reaction solution into cold water for 350 rn! ! The mixture was acidified with dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water (+50d×3) and dried (anhydrous Na2
5OJ, the solvent was distilled off, and the residue (93g) was distilled under reduced pressure.
p, 101-b Ethyl carboxylate 1; 4 g was obtained as a colorless oil.

'IINMRδppm ((:υC13): 1.13
~1.92 (1:Ill, [II, cycle.

hexyl-G2. C2', [:3. C3', C4,
G, °, C1, C5 °, C6, C,, ° and -[:00
GH2(:tl,), 2.22~2.35 (Il
l, ra, cyc 1ohexy I-(: ,
).

4.11 (2tl, q, , I=1711z, -Co
o(:ll2C1hl.

Ill (NeaLl: 1725c[l+
-5 (C=0).

(2) Synthesis of 1-cyclohexyl-5-phenyl-1,3-pentanedione 63 g of ethyl cyclohexanecarboxylate obtained in (1) (
0.4 mol) and 20 g of 4-phenyl-2-butane (
0.13 mol) and added sodium: 1. 1 g (0,1: 1 atom) was slowly added, and the reaction and post-treatment were carried out in the same manner as in Reference Example 5.
23g of coarse dark orange-red oil was added to the calanor fraction [silica gel: Fuco-gel C-200, solution: n-
Hexane/ethyl acetate-1oo/+-+I00/241
0o/a (V/V)] and l-cyclohexyl-5-
2.5 g of phenyl-1,3-pentanedione were obtained as a yellow oil.

+1NMRδppm((:Dl:+3): 1.(15
~1.8!1 (1011, m, cycle.

hexyl-C2, C2', G, , C3', C4
, I:4', C5, C5' J:6. (:6')2.
20-2.37 (III, +n, cyclohexyl
-C,), 2.65 (2H,t.

J=711Z, -CI12(:%C1]-), 2.90
(211,j, J□711z, 8r':!h-).

: 1.55 (211, s, -COCII, GO-: Keto type 1/20), 5.45 (Ill, s.

-C-CIIGO-: enol type 17/20), 7
．． 15-7.27 (511, m aromatic ring), 15.58 (
III, bs, -0 and (enol)).

JR (Neat): 1710cm” (C knee 0).

Example 28.5-(4-chlorosulfonylphenyl)
-1-cyclohexyl-2-diazo-! , 3pentanedione (in general formula [111].

1 (8=cyclohexyl group, Y=-502α1m°=2
) Synthesis of 0+ 1-Cyclohexyl-2-diazo-5-phenyl-1,3-pentanedione 1-Cyclohexyl-5phenyl-1,3- obtained in Reference Example 11 (2) 2.4 g of pentanedione (9,3
1.97 g of p-toluenesulfonyl azide obtained in Reference Example 1.
(10.2 mmol 1 was added dropwise at 0 to 5°C, and the reaction and post-treatment were carried out in the same manner as in Example I2 (1) to obtain 4 g of a crude yellow oil. This was separated by column separation [ Silica gel; Fuco-gel C-200, eluent: n-hexane/
Ethyl acetate = 100/l → 100/2 (V/V)]
1.9 g of L/,1-cyclohexyl-2-diazo-5-phenyl-1,3-pentanedione were obtained as a pale yellow viscous oil.

'HNMI? δppm (CDCl2): 1.18
~1.53 (6)1. o+, cycle.

hcxvl-G, ,C,°,C4,C4°,C5,
C, °) 1.68-1.82 (4H, +n.

cyc Iohexyl-1;2, ni2', C6
, C6'), 2.8:J~3.0011. m.

cyc1o1+cxyl-C, and -C112C112
(:0-) , :1.05~3.11(2+1゜m, A
r- to 1h-), 7.17~? Jl (5tl, m,
aromatic ring), IR (Nca): 2080c
m-' (-CN2), 1630 cm-' (C=0).

(215-(4-chlorosulfonylphenyl)-1-cyclohexyl-2-diazo-1,3-pentanedione (
In the general formula [1111, R8=cyclohexyl group,
1-Cyclohexyl-2-diazo-5-phenyl-1, obtained in Synthesis +11 of Y = -5O□α, +++' = 2)
Add 2.78 g of chlorosulfonic acid to a chloroporum solution containing 1.7 g of 3-pentanedione (6 millicells) dissolved in -N
] to -5°C, and the reaction and post-treatment were carried out in the same manner as in (2) of Example 12 to obtain a composite material 41) Omg
I got it. This was separated by column [silica gel: Wako gel C]
-200, eluent 20-hexane/ethyl acetate: 3/
I (V/V) I L/, 5-(4-chlorosulfonylphenyl)-1-cyclohexyl-2-diazo-1,
200 mg of 1-pentanedione were obtained as a pale yellow viscous oil.

111NMRδppIIl(CDCl3): 1.18
~1.64 (611, m, cycle.

heXyl-C3,C,l', C4,C4°, C5,C
5'), 1.67-1.90 (411, +n.

cyclot+exyl-C2,C2',C,,C6
°), 2.65-2.78 (dan, nl.

cyclohexyl-C,), 3.0M2)1. t
, J=711z, -el12C%GO-).

C20 (211, t, J=711z, her-Cr Lee,
-3,7,49(2H,d,,I・8t!z.

phenyl-G2. G, ), 7.95 (211, d
, J-811z, phenyl-[:a, GF,
).

fR (Neat): 2100cm-'(-CN2)
, 1640 cm-'((1:=0).

Example 29゜1,7-bis(4-chlorosulfonylphenylsyn-4-cyaso:1,5-heptanedione 3 obtained in Example 1)
g and baracresol novolac resin (molecular weight 10,000) 7
A photographic material A was obtained by stirring and dissolving 1.g and 5.0 g of diethylene glycol dimethyl ether in 50 g of diethylene glycol dimethyl ether.

A pattern forming method using a photosensitive material according to the present invention will be explained with reference to FIG. The photosensitive material A obtained above was spin-coated onto a substrate 1 such as a semiconductor, and after prebaking on a hot plate at 90° C. for 2 minutes, a photosensitive material film 2 with a thickness of 1.2 μq was formed.
I got it. (Figure 1(a)). Note that there is an insulation M on the substrate 1.
, a conductive film, etc. are often formed. Next 248.
4r+m excimer laser 4 was selectively exposed through a mask 5.

(Figure 1(b)). Finally, the exposed area of the photosensitive material film 2 is dissolved and removed by developing with a 20% aqueous solution of MP 2401 (manufactured by Sibley) for 60 seconds, and the resin pattern 2 is removed.
I got a. (Figure 1 (C)). The resin pattern 2a had a good shape with an aspect ratio of 90 degrees, and was a submicron pattern with a film loss of several percent or more. The surface of the substrate 1 was etched using this pattern 2a as an etching mask.

FIG. 2 shows the ultraviolet spectroscopy of this) IQ2 as a resist material. In addition, in Fig. 2, the solid line (-) indicates the line before exposure.
The broken lines (----) indicate the results for one exposed wheat. As is clear from this result, the change in transmittance after the exposed surface at 2.484 million m is a large value of about 74%, and this photosensitive material and the photosensitive compound of the present invention have a good response to rF excimer laser. You can see that he showed his sexuality.

Example 30゜4 g of 1,7-bis(4-chlorosulfonylphenyl)-4-diazo-3,5-heptanedione obtained in Example 1 and metacresol novolak resin (molecule 1i120,000) 8
A light-sensitive material was obtained by stirring and dissolving the following ingredients in 42 g of ethyl cellosolve acedate.

Using this, pattern formation and ultraviolet spectroscopy measurements were performed in the same manner as in Example 29, and good results almost equivalent to those in Example 29 were obtained.

Example 31゜ 3 g of 1-(4-chlorosulfonylphenyl)-3-diazo-2,4-pentanedione obtained in Example 12 and 7 g of baracresol novolac resin (molecule 11h) were dissolved with stirring in 50 g of diethylene glycol dimethyl ether. A photosensitive material was obtained.

Using this, pattern formation and ultraviolet spectroscopy ml+ determination were performed in the same manner as in Example 29, and almost the same good results as in Example 29 were obtained.

Example 32゜4 g of 6-(4-chlorosulfonylphenyl)-3-diazo-2,4-hexanedione obtained in Example 13 and 8 g of metacresol novolak resin (molecular weight 20,000) were added to 42 g of ethyl cellosolve acetate. A photosensitive material was obtained by stirring and dissolving.

Using this, pattern formation and ultraviolet spectroscopy measurements were performed in the same manner as in Example 29, and good results almost equivalent to those in Example 29 were obtained.

The resin in the photosensitive material is required to be highly transparent to far ultraviolet light, such as 248.4 na+, in order to reduce the light surface absorption of the photosensitive material. As resins other than those used in Examples 29 to 32, good results can also be obtained using styrene resins, maleimide resins, droxystyrene resins, orthochlorometacresol novolak resins, etc. It is not limited to Jl et al.

Similar transparency is required for the solvent, and diethylene glycol diethyl ether and the like can also be used.

Examples 33 to 62 The compounds of the present invention obtained in each example were used to prepare photosensitive materials using a photosensitive agent and ether.

These photosensitive materials were spin-coated onto a semiconductor substrate and prebaked to produce a photosensitive material film with a thickness of 1.0 μm, followed by an alkaline developer [2.38% tetramethylammonium hydroxide (TMAH) aqueous solution]. The dissolution rate was measured.

Further, pattern formation was performed in the same manner as in Example 29 using the above photosensitive material.

The results are also shown in Tables 1-1 and 1-2.

As is clear from the results in Tables 1-1 and 1-2, good patterns were obtained with each photosensitive material.

Furthermore, the dissolution rate of the films made with each photosensitive material was 400 nm/min or less, and the dissolution rate of the film made similarly using only poly(paravinylphenol) resin (molecular weight 7,000) (4,00 On+n /m1n), a very good value was obtained.

As is clear from this result, the compound according to the present invention has
It can be seen that it has the effect of reducing the rate of dissolution of photosensitive materials in alkaline developers.

Also, comparison of the results of Example 33 and Examples 34 to 37, comparison of the results of Example offenders and results of Examples 39 to 41, and comparison of the results of Example 46 and Example 47. Comparison with the results of ~56, comparison of the results of Example D with the results of Example 58, comparison of the results of Example 5 with the results of Example 6o, or comparison of the results of Example 6.1 with the results of Example 6. As is clear from the comparison with the results of No. 62, etc., in the compound according to the present invention represented by the general formula [1], there are two cases in which X and X' are mere hydrogen atoms and a case in which X and/or It can be seen that when using various substituents according to the present invention, the compound into which a substituent is introduced contributes more to the resistance of the photosensitive material to an alkaline developer.

Furthermore, among the photosensitive materials using the compounds according to the present invention having these substituents as photosensitizers, the one that has the highest resistance to alkaline developers is the photosensitive material of the present invention in which chlorsulfonyl or chlorosulfonyl is introduced as a substituent. It can also be seen that the photosensitive material contains such a compound.

In addition, a comparison of the results of Examples 33, 40, 42 and 45, a comparison of the results of Examples 34, 41, 43 and 45, a comparison of the results of Examples 46, 57, 59 and 61, or a comparison of the results of Examples 47 and 47. As is clear from the comparison of the results of 5B, 60 and 62, m and n in general formula [1] are larger, or in other words, the compound according to the present invention with a longer methylene chain is used in a smaller amount. The good results were obtained with 4iJ, which is probably due to its high sensitivity as a photosensitizer.

In addition, in actual h% 4'A million to 62, , ,
Similar results can be obtained using resins such as metacresol novolak resin, orthochlorometacresol novolac resin JIN, etc.

Example 6 A contrast-enhancing material for pattern formation having a composition of less than 3° was prepared.

1.7-bis(4-chlorosulfonylphenyl)-4-
Diazo-3,5-hebutanedione 4.0g para-cresol novolak resin (molecular weight 5,000) 2.
5g ethyl cellosolve acedate 20.0
g The patterned contrast-enhancing material thus prepared has a Krl of 248.4ron with a thickness of 0.12 μn when used as a patterned organic film.
'The difference in the i8 pass rate at 248.4 nm before and after exposure with an excimer laser was very large, more than 70%, and it was found that the contrast of the incident light was changed (movement).

FIG. 3 shows the process of resist pattern formation and lithography using the pattern-forming contrast-enhancing material according to the present invention.

3 positive resists (MP2400) on 1 substrate such as semiconductor
+ Sibley Co., Ltd.) to 1.5μrrN (3rd
Figure (a)). Next, on the positive resist 3F, a water-soluble organic film 6,
For example, a mixed solution of pullulan and polyvinylpyrrolidone is applied and formed. At this time, the mixing weight ratio of pullulan and polyvinylpyrrolidone was 4:1, and the film thickness at this time was approximately 0.1 to 0.3 μ% so as not to affect pattern formation. The water-soluble organic film as the intermediate layer is provided so that the lower resist layer and the upper pattern-forming organic film do not mix, and is not necessarily required (FIG. 3(b)). Next, layer 7 of the patterned contrast-enhancing material of the present invention was spin-coated to a thickness of about 0.12 Im. Here, the lower resist layer, the intermediate layer water-soluble organic film, and the water-soluble organic film and the F layer pattern forming 1r film were laminated with excellent adhesion. Then, reduction projection exposure method (5:1 reduction, NA
= 0.36) via mask 5 selectively i1:2
48. Expose with 40mKrF excimer laser 4 (
Figure 3 (C)). Then, the pattern forming contrast enhancer 7 of the present invention, which is a layer of contrast enhancement, and the water-soluble organic film 6, which is an intermediate layer, are simultaneously removed using an ordinary alkaline developer.
was developed to form a resist pattern 3b (Fig. 3 (
d)). At this time, the resist pattern 3b was able to resolve lines and spaces of 0.3 μm with improved contrast (aspect ratio 89°).

In the examples, the compounds of the present invention obtained in Examples 2 to 28 were used as photosensitizers instead of 1,7-bis(4-chlorosulfonylphenyl)-4-diazo-3,5-hebutanedione. Even if 1)+5' is used, the same result can be obtained.

(Effects of the Invention) The present invention provides a novel photosensitive compound having excellent reactivity to, for example, 248.4 nm excimer laser radiation, a photosensitive material containing this compound, and a pattern forming method using stiffness. The photosensitive material using the photosensitive compound according to the present invention can be exposed to deep ultraviolet light (Deep I) such as KrF excimer laser (248,4 nm)
JV) Since it can be used as an exposure resist or contrast, it is of great value for forming ultra-micro patterns in the semiconductor industry, etc.

[Brief explanation of the drawing]

FIG. 1 is a process cross-sectional view of the pattern forming method of Example 29 using the photosensitive material containing the compound of the present invention, and FIG.
FIG. 3 is a cross-sectional view of the pattern forming method of Example 63, and FIG.
400) Process sectional view of the pattern forming method using
The figure is an ultraviolet spectral characteristic diagram of MP2400 (7) near 248.4 nm (where the solid line is the exposed area and the broken line is after exposure). DESCRIPTION OF SYMBOLS 1... Substrate, 2... Photosensitive material film for pattern formation, 3
...Posiresist W, 4-K rF excimer laser,
5...Mask, 2a, 3b...Resin pattern, 6.
...Water-soluble organic film, 7...Contrast enhancement material film for pattern formation. Figure 1 Figure CO Fumanaga (nm) Figure Figure Figure Harunaga (nm)

Claims (9)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, X is a hydrogen atom, -SO_3R^1 (However, R^
1 represents an alkyl group. ), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, R^2 and R^3 each independently represent a hydrogen atom or an alkyl group that may have a substituent, or R^2, R^3 and N may form a ring such as a piperazine ring, piperidine ring, pyrrolidine ring, or morpholine ring) or a functional group that can react with a resin, and R is an alkyl group or a cycloalkyl group. , a hydroxyalkyl group, an alkoxyalkyl group, or ▲a mathematical formula, a chemical formula, a table, etc.▼ (however, X
' is a hydrogen atom, -SO_3R^4 (however, R^4 represents an alkyl group), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (however, R^
5, R^6 each independently represents a hydrogen atom or an alkyl group which may have a substituent, or R^5, R^6
and N may form a ring such as a piperazine ring, piperidine ring, pyrrolidine ring or morpholine ring. )
Or represents a functional group that can react with a resin. Further, n represents a natural number. ), m represents a natural number. ] A photosensitive material characterized by containing a photosensitive compound represented by the following. (2) The photosensitive compound represented by the general formula [I] has the general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, Y is a hydrogen atom, -SO_2Cl, -SO_2B
r, -SO_3R^1, -SO_3H or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^1, R^2 and R^3 are the same as above. Also, -SO_2Cl, -SO
_2Br and -SO_3H include their quaternary salts. ),
R^7 is an alkyl group, cycloalkyl group, hydroxyalkyl group, alkoxyalkyl group, or ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ represents {however, Y' is a hydrogen atom, -SO_2Cl, -S
Represents O_2Br, -SO_3R^4, -SO_3H or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^4
, R^5 and R^6 are the same as above. Also, -SO_2C
l, -SO_2Br and -SO_3H include their quaternary salts. ). Further, n' represents an integer from 1 to 20. }, m' is 1~
Represents an integer of 20. ] The photosensitive material according to claim (1), which is a compound represented by the following. (3) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, X, R and m are the same as above. ] After applying a photosensitive material containing a photosensitive compound and resin shown in ] onto a substrate,
A pattern forming method characterized by forming the photosensitive material pattern by exposing to deep ultraviolet light and developing. (4) The photosensitive compound represented by the general formula [I] has the general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, Y, R^7 and m' are the same as above. . ] The pattern forming method according to claim (3), wherein the compound is a compound represented by: (5) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, X, R and m are the same as above. ] After forming a thin film of a photosensitive material containing a photosensitive compound and a resin represented by the above on a resist on the surface of a substrate, it is exposed to deep ultraviolet light, developed, and the layer of the photosensitive material is removed. A pattern forming method characterized by forming a resist pattern. (6) The photosensitive compound represented by the general formula [I] has the general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, Y, R^7 and m' are the same as above. . ] The pattern forming method according to claim (5), which is a compound represented by the following. (7) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] [In the formula, Y, R^7 and m' are the same as above. ] A compound represented by. (8) The compound represented by the general formula [II] has the general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] [In the formula, R^8 is an alkyl group, a cycloalkyl group, a hydroxyalkyl group, or represents an alkoxyalkyl group,
Y and m' are the same as above. ] is a compound represented by
A compound according to claim (7). (9) The compound represented by the general formula [II] has the general formula ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ [IV] [In the formula, Y, Y', m
' and n' are the same as above. ] is a compound represented by
A compound according to claim (7).