JPH0355549A - Novel photosensitive compound - Google Patents

Abstract

PURPOSE:To improve the photoreactivity with 248.4nm excimer laser by using compds. having specific structures. CONSTITUTION:The compds. expressed by formula I, formula II and formula III are used. In the formulas I to III, X denotes a hydrogen atom, -SO2Cl, -SO2Br, -SO2N-R<3>-R<4>, -SO3H or -SO3R<5>; R<3>, R<4> respectively independently denote a hydrogen atom, alkyl group which may have a substituent or R<3>, R<4> and N may form a ring, such as piperazine ring, piperizine ring, pyrrolidine or morpholine ring, etc.; R<5> denotes an alkyl group. Y denotes a hydrogen atom, alkyl group, alkoxy group or halogen atom; Z denotes a hyrogen atom, alkyl group, alkoxy group or halogen atom. X' is the same as X; Y' as Y, Z' as Z and m and n denote 1 to 20 integer. The photoreactivity with 248.4nm excimer laser is extremely improved in this way.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel photosensitive compound useful as a photosensitizer for photolithography used, for example, 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 KrF excimer laser (248.4 nm) is being considered. It's getting to the point where it's being done. 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 KrF 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 with reference to FIG. After doing this, a resist film 3 having a thickness of 1.2 μm is obtained {4th
Figure (a)}. Next, a 248.4 nm κrF excimer laser 4 is selectively exposed through a mask 5 {Fig. 4(b)
)}. Finally, 20 of MP2401 (manufactured by Sibley)
% aqueous solution (alkaline) for 60 seconds, the citrus pattern 3a is obtained {Figure 4 (C)}
. However, when using MP2400, the sensitivity to light of this wavelength is poor, 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 was significantly deteriorated, and an aspect ratio of only about 60 degrees was obtained. The reason why the pattern shape is so poor is considered to be due to the large surface absorption of the exposure light of the MP2400 resist. This is because the main polymer (resin) used in the resist itself has a large light absorption property for exposure light, or the photoreactivity of the photosensitive material in the resist is poor. That is, naphthoquinonediazide-based photosensitive materials used in conventional resists generally have a wavelength of 248.4 nm.
The absorption of nearby light is large, and the transmittance after exposure is hardly improved. For example, MP of film thickness I JLII
2400, κrF excimer laser (248.4n
The change in light transmittance before and after exposure using Il) is only about a few percent at 248.4 nm, as shown in FIG. 5, and it is understood that the reactivity is poor. Therefore, the present situation is such that the appearance of a photosensitive material that is more reactive to the 248.4 nm excimer laser, or in other words, the appearance of a photosensitive agent that is more photoreactive to the same laser, is eagerly awaited. Photosensitizers developed for this purpose include, for example, compounds having the groups shown by Gray (US Pat. No. 4,622,283).
However, in the compounds specifically disclosed in this patent specification, the functional groups at both ends of the group described above are simple alkyl groups, aryl groups, or both ends are bonded to form an alkylene ring. When resists containing these compounds as photosensitizers are used in photolithography, it is unlikely that they will have a strong blocking ability against alkaline developers in unexposed areas, resulting in a large amount of resist film loss. , it is predicted that the contrast will decrease accordingly.
It is difficult to say that it is necessarily a practical photosensitizer. (Object of the invention) The present invention was made in view of the above-mentioned circumstances, and
The purpose of the present invention is to provide a novel photosensitive compound that has significantly excellent photoreactivity to 8.4 nm excimer laser. [Structure of the Invention] The present invention represents the general formula [1] -SO3H or -SO3R5 (provided that 13.
R4 each independently represents a hydrogen atom or an alkyl group which may have a substituent, or R3. R4 and N may form a ring such as a viperazine ring, a biverizine ring, a virolidine ring or a morpholine ring, and R5 represents an alkyl group. Moreover, -SO2CI, -SO28r and -503H include their quaternary salts. ), Y is a hydrogen atom,
Represents an alkyl group, an alkoxy group, or a halogen atom (however, H6, R? each independently represents a hydrogen atom or an alkyl group which may have a substituent, or 16.
R7 and N may form a ring such as a biverazine ring, a biverizine ring, a virolidine ring or a morpholine ring, and R8 represents an alkyl group. Also, −So2CI, −
SO2Br and -SO,H include their quaternary salts. ),
Y° represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and 2° represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. }, m, Qbin is 1
Represents an integer of ~20 (excluding cases where Y and Y° are both hydrogen atoms). ] This is an invention of a compound represented by. is an integer from 1 to 20. Furthermore, bases that can form quaternary salts with R1 include, for example, ammonia, pyridine, biverazine, biperidine,
N-methylpyrrolidine, morpholine, an atom such as a methyl group. Alkyl groups (which may be linear or branched) such as ethyl group, proyl group, butyl group, amyl group, hexyl group, hebutyl group, octyl group, nonyl group, decyl group, or these alkyl groups Examples include those in which a substituent such as a hydroxyl group or an alkoxy group (eg, methoxy group, ethoxy group, etc.) is attached to the group, and Rs. R4 and N may form a ring such as a biverazine ring, a piverizine ring, a virolidine ring, or a morpholine ring. -S.O. R5 in R5
For example, methyl group, ethyl group, proyl group. Butyl group. Amyl group, hexyl group, heptyl group. Octyl group, nonyl group. Examples include alkyl groups (which may be linear or branched) such as decyl group. Further, Y in R' and Y in R2 are hydrogen atoms, such as methyl group, ethyl group, proyl group, butyl group, amyl group, hexyl group, hebutyl group, octyl group, nonyl group, decyl group. Alkyl groups (which may be linear or branched) such as methoxy, ethoxy, propoxy, and butoxy groups. Alkoxy groups such as amyloxy group, hexyloxy group, hebutyloxy group, octyloxy group, nonyloxy group, decyloxy group (which may be linear or branched), halogen atoms such as iodine, bromine, chlorine, etc. may be the same or different (however, except when Y and Y" are both hydrogen atoms), and 2 in R' and 2' in R2 are hydrogen atoms. atoms, such as methyl group, ethyl group, probyl group, butyl group, amyl group, alkyl group such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc.
It can be either straight or branched. ), for example, methoxy group, ethoxy group, propoxy group, butoxy group. Amyloxy group, hexyloxy group, hebutyloxy group, octyloxy group, nonyloxy group. Alkoxy groups such as decyloxy groups (which may be linear or branched),
Examples include halogen atoms such as iodine, chlorine, and bromine, which may be the same or different. In addition, hydrogen -S01R8 is mentioned as X° in R2, -so2C
i, -SO2Br and -SO3H may be their quaternary salts, and bases that can form quaternary salts with them include, for example, ammonia, pyridine, piperazine, piperidine, N-methy group, ethyl group. , proyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group (which may be linear or branched), or to these alkyl groups. Examples include those with substituents such as hydroxyl group, alkoxy group (eg, methoxy group, ethoxy group, etc.), and R6. R7 and N may form a ring such as a biverazine ring, a piverizine ring, a virolidine ring, or a morpholine ring. -5
R8 in 03R8 is, for example, a methyl group, an ethyl group, a probyl group, a butyl group, an amyl group, a hexyl group, a hebutyl group, an octyl group. Examples include alkyl groups (which may be linear or branched) such as a nonyl group and a decyl group. The compounds of the present invention represented by the general formula [1] include compounds represented by the following general formulas [II], [1, and [IV]. (In the formula, x, x', Y, Y', m and n are the same as above.) (In the formula, X, X', Y, 2', m and n are the same as above.) (In the formula, x, x', Z, 1", m and n 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 [11] as an example. ( In the formula, Y, Y', m and n are the same as above.) (In the formula, Y; Y', m and n are the same as above.) (In the formula, M and M' both represent -S02α , or one of which represents -So2Cl and the other represents a hydrogen atom; Y, Y', m and n are the same as above.) That is, first, a compound represented by the general formula [n-1] C, hereinafter abbreviated as compound (II-1)) is reacted with a diazotizing agent in the presence of a base to form a wooden invention compound (hereinafter, compound [11
-2]. ) is obtained, and then when this is reacted with chlorosulfonic acid, a compound of the general formula [II1 in which both X and X" are -SO2a, or one of which is -SO2α and the other is a hydrogen atom The invention compound is obtained. The diazotization reaction is usually carried out by combining compound [II-17 and compound #[
II-17 0.5 to 3 mol, preferably 0.8 to 1.5 mol of diazotizing agent per mol of compound [II
[-1] 0.5 to 5 mol per mol, preferably 0.8 to 1.5 mol of base in a suitable reaction solvent, -
10 to 30°C, preferably -5 to 10°C for 15 minutes to 5
This is done by reacting for a period of time, preferably 1 to 2 hours. Examples of reaction solvents used in the diazotization reaction include alcohols such as ethanol and isoprobanol;
For example, ethyl ether. Ethers such as isopropyl ether and tetrahydrofuran, such as methylene chloride. Examples include halogenated hydrocarbons such as chloroform, carbon tetrachloride, and 1,2-dichloroethane, hydrocarbons such as n-hexane, cyclohexane, and toluene, and examples of diazotizing agents include p-toluenesulfonyl azide and benzene. Examples include sulfonyl azide, 2-azido-3-ethylbenzothiazolium fluoroborate, and examples of the base include viveridine, triethylamine. N-methynorehydrolidine, N-methynoremonorephorin, pyridine. Organic bases such as diethylamine, e.g. NaOCH3
, NaOC2H5, κQC(C}13)3, KOC
Examples include alcoholates such as 2t{s, sodium metal, sodium hydride, potassium hydride, and the like. In addition, the chlorosulfonation reaction is performed using the compound [ n -2]
and 1 to 20 mol, preferably 2.5 to 9.0 mol, of chlorosulfonic acid per 1 mol of compound [II-21] in the presence or absence of a solvent at -20 to 20°C, preferably -1O to 5 ℃ for 15 minutes to 5 hours, preferably 1 to 2 hours.
All you have to do is let it react over time. As a reaction solvent used in the chlorosulfonation reaction, does it not inhibit the chlorsulfonation reaction and can itself be chlorosulfonated? There are no particular limitations on organic solvents as long as they are free of organic solvents, such as carbon tetrachloride, ethane tetrachloride, etc. Halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, methylene chloride, carbon disulfide, etc.
Usually preferred. SO20 obtained in this way! For example, if the body is hydrolyzed by a conventional method, the general formula [1F, X, X'
is -SO, H (or either X and ×゛ is -50,
I+ te and the other ka-SOzCl), or X and X'+7
) A compound of the present invention is obtained in which one of the atoms is -5038 and the other is a hydrogen atom. Also, if alcoholysis is performed instead of hydrolysis, X is -S03R5 (R' is the same as above) and X° is -503R8 (R8 is the same as above) (or either X and is -SO3R5 (R8) and the other is -SO■ (f), or either × or X゛ is -
A compound of the present invention in which the other is a hydrogen atom in SO3RS (R8) is obtained. Furthermore, instead of hydrolysis or alcoholysis, the SO2a form can be treated with ammonia or, for example, monomethylamine. Monoethylamine, monobrobylamine, monobutylamine, monobenthylamine, dimethylamine,
Diethylamine. Dibrobylamine, monoethanolamine. Aliphatic amines such as diethanolamine and the compounds of the present invention are obtained. Compound [11-1] is, for example, a compound represented by the general formula (wherein Q represents a chlorine atom, a bromine atom, or an iodine atom, and Y and m are the same as above) and a general formula "G(CH2). -1-Q [In the formula, Q, Y' and n are the same as above] and 2,4-pentanedione are mixed in a solvent such as cyclohexane, n-hexane, toluene, isobrobyl ether, etc. , for example n-butyllithium.lithium diisobrobylamide.lithium, l.1.l,3,3.
3-hexamethyldisilazane, KH/n-BuLi,
It can be easily obtained by reacting with a condensing agent such as NaH/n-BuLi at a low temperature, for example, 10° C. or lower, so it is sufficient to use the product obtained in this way. In addition, the compound [■-111 is, for example, the general formula (in the formula, Y
and m are the same as above. ) and esters represented by the general formula (in the formula, R represents an alkyl group, and Y and n are the same as above) are combined with sodium metal, sodium hydride, metal alkoxide, etc. Since it can be easily obtained by carrying out a condensation reaction in the presence of the compound, the product obtained in this manner may also be used. Other compounds of the present invention can also be synthesized by similar methods. That is, for example, instead of compound [■-11, compound represented by the general formula [II[-1] (wherein, Y, Z', m and n are the same as above) (hereinafter, compound [II1-1]) The compound of the present invention represented by the general formula [[] can be easily obtained by using the compound [II-1] as a starting material and performing the synthesis according to the synthesis method described above. , general formula [IV-
13 (wherein Z, Z', m and n are the same as above) (hereinafter abbreviated as compound [IV-1])
The compound of the present invention represented by the general formula [■] can be easily obtained by performing the synthesis according to the above-mentioned synthesis method using as a starting material. Compound [II1-1] and compound [IV-1] can be easily obtained by synthesizing compound [II-1] according to the method for synthesizing compound [II-1], so it is sufficient to use those obtained in this way. That is, compound [II1-1] is, for example, a compound represented by the general formula (wherein Y, Q and m are the same as above) and the general formula IcO(cH2). The above compound [1
-1], or for example, a ketone represented by the general formula (wherein YFjL and m are the same as above) and a general formula (where l゜, R゛ and It can be easily obtained by condensation reaction of esters represented by (n is the same as above) according to the synthesis method C of the above-mentioned compound [11-11], so it is sufficient to use the compound obtained in this way. Compound [IV-1] is, for example, a compound represented by the general formula (wherein Z, Q and m are the same as above) and a compound represented by the general formula 2''-co-(CH2)n-1-Q (formula 2, Q and n are the same as above) and 2,4-pentanedione are combined into the above compound
I-1], or by performing a condensation reaction according to the synthesis method of [I-1], or, for example, by using a ketone represented by the general formula (wherein Z and m are the same as above) and the general formula? In the formula, 2°, R′ and n are the same as above. ) can be easily obtained by subjecting them to a condensation reaction according to the synthesis method of the above-mentioned compound [1-11], so it is sufficient to use the compound obtained in this way. The compound of the present invention represented by the general formula [11] has a wavelength of 248.4 nm.
Highly responsive to light. That is, the change in transmittance before and after exposure is large (approximately 50% or more), and the transmittance after exposure is also as large as 70% or more. Furthermore, in the general formula [I], R
At least one of X of l and X゜ of R2 is -SO■
α, -so■B ``or -SO. A compound that is H -OH
When a photosensitive material mixed with a resin containing a group is heated after coating, a crosslinking reaction proceeds, which has the effect of reducing the solubility of the resin in a developer. Therefore, by using this as a material for a resist or the like, a well-shaped resin pattern can be obtained. Ultraviolet light (Deep UV light) For example, excimer laser? It becomes. Therefore, in the photosensitive material containing the compound of the present invention, only the previously irradiated portion becomes alkali-soluble, 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 the resin used is mainly an alkali-soluble novolak resin. Therefore, it is desirable that the photosensitive material can suppress the alkali solubility of the novolak resin in the unexposed area. In general formula [I], at least one of X in R1 and ×° in R2 is -SO2α, -50,Or or -5031
1, the photosensitive compound has -SO■α at the terminal group.
, -SO■Br, -SO. Since one or two functional groups such as H are present, crosslinking proceeds to form bonds in the alkali-soluble portion of the resin by heating, thereby suppressing the alkali solubility of the resin. Therefore, when used in photosensitive materials, the problem of film thinning in unexposed areas can be significantly improved. Furthermore, since the compound of the present invention has a methylene chain such as iGH2)- in its molecule, the entire molecule is stabilized, which improves the thermal stability of the compound of the present invention. . and. This also makes the compound of the present invention a substance that has excellent storage stability and can be industrially mass-produced. The substitution position on the benzene ring may be any of the 2nd to 6th positions when the methylene group is the 1st position, and the substitution position on the naphthalene ring is also the 2nd to 8th position in the case of a 1-naphthyl group. In the case of a 2-naphthyl group, it may be at the 1st or 3rd to 8th positions, and there is no significant difference in the effect as a photosensitizer in either case. Also, the length of the methylene chain is m = 1 ~ 20, n = 1 ~
Similarly, there is no significant difference in the effect of any of the 20 combinations. The present invention will be described in more detail below with reference to reference examples, examples, and application examples, but the present invention is not limited in any way by these. [Example] Reference example 1. Synthesis of p-toluenesulfonyl azide (tosyl azide) After dissolving 22.5 g (0.35 mol) of sodium azide in a small amount of water, 90% aqueous ethanol 1:] O
mf! diluted with Next, an ethanol solution in which 60 g (0.32 mol) of p-toluenesulfonyl chloride was dissolved was added dropwise at 10 to 25°C, and the mixture was reacted with stirring 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 over anhydrous MgSO4. The drying agent was removed to obtain 50.7 g of p-toluenesulfonyl azide as a colorless oil. ' }INMRδP ffi (CDQ 1) '
2-4 3 (3H,S:CHz)
> 7 - 2 4 (2H, d, J・8Hz,
phenyl-C3. Os), 7.67 (2
}1, d, J-8Hz. phenyl-C2. C6)
. IR (Neat): 2120cm” (-N3)
. Reference example 2.1.7-bis(4-methylphenyl)-3.
Synthesis of 5-heptanedione 60% sodium hydride in cyclohexane +00rnl 1.
2.4-
A cyclohexane solution in which 195.2 g (1.95 mol) of bentanedione was dissolved was added dropwise, and the mixture was stirred and reacted at the same temperature for 40 minutes. Then, after injecting 483 g of N,N,N',N'-tetramethylethylenediamine, the n
-Butyllithium! ．． 6M n-hexane solution 177
8 g was added dropwise, the temperature was further raised to room temperature, and the mixture was reacted for 24 hours. Next, 635.4 g of 4-methylbenzyl chloride was added dropwise to this reaction solution at 0 to 5°C, and after being left overnight, it 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 drying agent, the solvent was distilled off to obtain 568 g of an orange-red oil, which was recrystallized from ethanol to give 1.7-bis(4-methylphenyl)-3.
．． 155 g of 5-hebutanedione were obtained as white needles. mp. 74.8-75.7°C. ! 11NMRδI)l)In(CDCft3): 2
J1(6!t,s,Ar-%X2),2.55(
4}1, t, J・8Hz, Ar-cH. (:H, (
:O-X 2), 2.88(4t{,t, J-8Hz
, Ar-C! LICH211:0-X 2), 3.
50 (2H, s.-GOCH.GO-: Keto type 1/
10) ,5.43(IN,s, -C=CH-co-
: Enol type 9/10), 7.04 ~ 7.11
(8N, m. aromatic ring x 2), 15.43 (IH, b
s, -Q(enol)),IR (KBr vI.)
: 1620cm-' (G-Q). Example 1.1.7-bis(3-chlorosulfonyl-4-
methylphenyl)-4-diazo-3,5-hebutanedione (in general formula [II], Y-Y'-CH3, X-
X'=-so. ct, msn. Synthesis of compound 2) (
1) Synthesis of 1.7-bis(4-methylphenyl)-4-diazo-3.5-hebutanedione 1.7-bis(4-methylphenyl)-obtained in Reference Example 2
After dissolving 112.8 g (366 mmol) of 3.5-heptanedione in methylene chloride 73 (7!IC) and adding 31.1 g (366 mmol) of viveridine,
p-toluenesulfonyl azide 75 obtained in Reference Example 1 at ℃
．． 6 g (380 mmol) was added dropwise, and further 2 g (380 mmol) was added at the same temperature.
The reaction was stirred for hours. Is the reaction solution diluted in caustic potash water? After washing with water, it was washed several times with water and dried with anhydrous MgSO4. After removing the drying agent, the solvent was distilled off to obtain 129 g of a brown oil. The residual oil was then recrystallized from ethanol and! ,7
'-Bis(4-methylphenyl)-4-diazo3,5
-103 g of hebutanedione was obtained as pale yellow prism crystals. mp. 45.6-46.8°C. 'HNMRδppm (CDα3): 2.31 (6}
1, S, Ar-CHX 2). 2. 88-3. 0
5 (8H, m, Ar-GJC%GO-X 2).
7. 10 (8N, s. aromatic ring x 2). IR(κBri): 2100cr'(-CN2), 1
660c ``' (C ■ 0). t2) 1,7-bis(3-chlorosulfonyl-4-methylphenyl)-4-diazo 3,5-hebutanedione (general formula [11]i.: Y-Y' tone-(:H3,
Compound of X'X"-SO2C1, tn-n■2 1.7- obtained in 1)
A chloroform solution containing 90 g (269 mmol) of bis(4-methylphenyl)-4-diazo-3.5-heptanedione dissolved therein 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 5.5 mL of ice water, extracted with chloroform, and the separated chloroform layer was collected. After washing with water twice, it was dried with anhydrous MgSO4. After removing the desiccant, the solvent was distilled off to obtain an oily residue. The oil was then separated into columns.
[Silica gel: Wakogel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.), eluent: n-hexane/ethyl acetate = 1/1
(v/v) ] t,, 1,7-bis(3-chlorosulfonyl-4-methylphenyl)-4-diazo 3,5-
30 g of hebutanedione were obtained as a pale yellow viscous oil. 'I-INMRδppa+(CDCta): 2.7
4 (6H,s,Ar-CH,x2) ,3.04
~3.08 (8B, m, Ar-C% CHIGO-x2)
, 7.34 (211, d, J■8Hz. pheny
l-C,,x2). 7.49 (2H, dd, J-2H
z and J-8Hz, phenyl-GsX2), 7
．． 90 (28, d, J・2Hz. phenyl-C.
X2). IR (Neat): 2110cm-' (CN2)
, 1650cm-' ((:■0).UV(CH3CN)λa+ax(ε): 233.
1r+n+(27550). Elemental analysis value (C21H20α2N20 [IS2) theoretical value: C%, 47.46: Hne, 3.79; N! !
, 5.27 Actual value: C$, 47.54; H main, 3
．． 99. N! Ii, 5.21, Example 8 2.1.7-bis(3-methoxysulfonyl-4-methylphenyl)-
4-diazo 3,5-hebutanedione (general formula [II]
In , Y=Y'=-CH. t. X・X'・-SO
3CH3. Synthesis of Example 1 (compound m-n72)
2) 1,7-bis(3-chlorosulfonyl-4-
3.1 g (5.8 mmol) of methylphenyl)-4-diazo-3.5-heptanedione was dissolved in 25 methanol and 40 methylene chloride, and 1.7 g of triethylamine was added dropwise thereto at 5 to 10°C. After reacting with stirring at room temperature for 8 hours, the residue was concentrated under reduced pressure and diluted with methylene chloride 36 (lat!). After washing several times with water, anhydrous Mg
Dry with SO4. After removing the desiccant, the solvent was distilled off, and the remaining crude oil (2.9 g) was separated by column [silica gel: Wakogel C-200, eluent: n-hexane/ethyl acetate = 5/
1 → 3/1 -) 2/1 (V/V)] L/, 1.7
1.9 g of -bis(3-methoxysulfonyl-4-methylphenyl)-4-diazo-3,5-hebutanedione was obtained as a pale yellow viscous oil. 'HNMRδppm (CDα3): 2.60 (
6}1, S, Ar-i1l, X 2), 3.01 ~ 3
．． 05 (8M, m, Ar-CIjICii, Go-X2
). 3.74(6H,s,-SO3CHix2),
7.28 (2H, d, J-8Hx, phenyl-
Cs x2), 7.40 (2B, dd, J-8Hz
, and J12}1x, phenyl-C6x 2)
．． 7.82 (2tl,d,J-2Hx.phenyl
-C2X 2). In(Neat): 2120cm-'(1;N,
), 1640cm-' (C-0). UV (CH3(:N) λmax(ε) :225
．． 4nl1l (29060). Elemental analysis value (CzzHzsNzOA5z) Theoretical value: C
%, 52.86. 8'! , 5.01. rl,
5.36 Actual value: C! k, 52.74: H%,
5.24. N! k, 5.26. Example 3.1.7-bis(3-ethoxysulfonyl-4
-methylphenyl)-4-diazo-3,5-hebutanedione (general formula [II], Y-Y'-OH,,
Synthesis of 1.7-bis(3) obtained in (2) of Example 1
-Chlorsulfonyl-4-methylphenyl)-4-diazo 700 mg (1.3 mmol) of 3,5-hebutanedione dissolved in 201 ethanol and 80 methylene chloride was added with triethylamine 365B at 5 to 10°C.
was added dropwise, and the reaction and post-treatment were carried out in the same manner as in Example 2 to obtain crude oil 700B. This is separated by column [
Silica gel: Wakokel C-200, eluent: n-hexane/ethyl acetate = 571 -+3/! (v/v)]
450 mg of L/,197-bis(3-ethoxysulfonyl-4-methylphenyl)-4-diazo-3,5-heptanedione was obtained as a pale yellow viscous oil. 'HNMRδppm (CDCi3): 1.32 (
6H, t, J・7Hx, -SO3CH2CH1x2),
2.61 (6H, s, Ar-ell, x2),
3.01-3,08 (8H, m, 8r-CHCHCO-
X2), 4.10 (4H,q,J-7HZjS
03CtjlCH3X 2). 4.27 (2H,
d, Js8Hz, phenyl-C,, x 2), 7.
39 (2H, dd, J・2Hz and J-8Hz, ph
enyl-Csx 2) 7.82 (2H, d, J・2H
z, phenyl-C2x 2). IR (Neat)
: 2110cm” (CN2), 1645cm
-' (C-0). UV(Cll3CN)λmax(ε): 225. 4
nm (309 10). Elemental analysis value (C2sHsoN20sS2) theoretical value:
C%, 54.53: H%, 5.49. N turtle, 5
．． 09 actual measurement value: C! 6.54.46; H turtle, 5
．． 56; N96, 5.14. Example 4.1.7-bis(3-N,N-diethylaminosulfonyl-4-methylphenyl)-4-diazo3.
5-hebutanedione (in the general formula [03, Y-Y'.
1(:H3,X・X'・-SOzN(hhh. m −
Compound 1 obtained in step (2) of Synthesis Example (2)
7-bis(3-chlorosulfonyl-4-methylphenyl)-4-diazo 3,5-hebutanedione 700mg
(1.3 mmol) was dissolved in acetonitrile 15-
1 g of N,N-diethylamine was added dropwise at 5-10°C. Then, after reacting with stirring at room temperature for 10 hours, it was concentrated under reduced pressure.
The residue was diluted with 40% methylene chloride, washed several times with water, and then anhydrous M
Dry with gSO4. After removing the desiccant, the solvent was distilled off, and 800 mg of the crude oil residue was separated by column separation [silica gel: Wako gel (: -200, eluent: n-hexane/ethyl acetate = 5/l → 2/l (v/v )1-bis, 1.7-bis(3
-N,N-diethylaminosulfonyl-4-methylphenyl)-4-diazo 3,5-heptanedione 380t
Ag was obtained as a slightly yellow viscous oil. IHNMRδI)Pln(CDCt3): 1.12
(1211.t, J・7Hz, N-CH2C!lLlx
4), 2.55(61{,s,Ar-CHx2),
2.96 to 3.08 (8H, n+, -GHCi(:O
-X2), 3.30 (811,Q,J・7HZ,N
~C CIL + X4), 7.20 (2H, d, J・8
Hz, phenyl-(:,X2), 7.28(2H
, d, J・8tlZ, phenyl-C6X2),
7.76 (2H, s, phenyl-C, X2). IR (Neat): 2120c'' (-CN2)
, 1650c ``'{CW=0). UV (C, H3CN) λwax (ε): 227
．． 2r+m (30810). Elemental analysis value (CzqH4oN406S2) theoretical value:
C96, 57.59; H! ! , 6.67: N%.
9.26 Actual value: C*, 57.71. H turtle,
6.42: No! Ii. 9.50. Example 5.1.7-bis(4-methyl-3-sulfophenyl)-4-diazo3.5-hebutanedione (in general formula [II], Y-Y'-GH3, X-X' 1.7-bis(3-chlorosulfonyl-4-methylphenyl)-4-diazo obtained in {2) of Example 1 3.5-hebutanedione 1 .4 g (2.6 mmol) in tetrahydrofuran 401d and water 40FRl;
The reaction was stirred at room temperature for 48 hours. After washing the reaction solution several times with methylene chloride, it was dried under reduced pressure to obtain 1,7-bis(4-methyl-3-sulfophenyl)-4-diazo-3,5-hebutanedione l. 2 g were obtained as a pale yellow viscous oil. I HNMRδpp@(GOα,-DMSO-d.)
: 2.48 (6H, s, bx 2). 2.80
(4H.t, J.7Hz.-CjjlGO-x 2)
．． 3.04 (4H, t, J・7Hz.8r-Ch-
X 2) , 4.98 (2H, bs, -SOs!jx
2), 7.02-7.14 (4H, m, phenyl
-CsJ:6X2), 7.60(2tl,s,phe
nyl-G2x 2). IR (Neat): 2110cm-I (-CN2)
, 1630 cm-' (G-0). Elemental analysis value (C2+Ht2N20aSz) theoretical value: (
J, 51.00. H$, 4.48. N! 4, 5
．． 66 Actual value: C! k, 50.82; H%, 4
．． 73. N! k, 5.93, Example 6.1.7-
Bis(4-methyl-3-sulfonatophenyl)-4-diazo 3,5-hebutanedione diammonium salt (general formula

[■ In 1, Y-Y'・10H3, X=X'・-
1.7-bis(4-methyl-3-sulfophenyl)-4-diazo 3.5-hebutanedione obtained in Example 5. Og
(2 mmol) was dissolved in acetonitrile 27-, and 0.55 g of a 28% ammonia aqueous solution was added dropwise thereto at 0 to 5°C, followed by stirring at the same temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and the residual liquid was washed with acetonitrile several times and dried under reduced pressure to give 1,7-bis(4-methyl-3-sulfonatophenyl)-4-diazo3.5-hebutanedione diammonium salt 950
IIlg was obtained as a pale yellow viscous oil. 1 11NMRδI)pm(CDCl3-DMSO-d
a) :2.60 (6H,s,C!hX?), 2
．． 83 (4H, tj・7Hz, -ftjzCO-
2), 3.06 (4Lt, J■7Hz, Ar-C
! lLl-x2), 4.74 (88, bs. NLL4
'l. 07 (4N.s, phenyl-C6, C6X
2), 7.06 (2N, s.phenyl-C2x
2). (R(Neat): 33QOcm” (NH4)
, 2090cm-' (-CN.) , 1620cr
'(C・0). Elemental analysis value (C2+H2aNaOaSz) theoretical value: (
J, 47.72. 8 turtles, 5.34: N! Ii
,IO. Iio actual value: CX, 47.50. H turtle, 5.51; N *, 10.91, Reference example 3.1.
Synthesis of 2-di(l-naphthyl)-3.5-hebutanedione 27g of 60% sodium hydride was charged in 320ml of cyclohexane, and 59.6g (0.595g) of 2.4-bentanedione was added at 20-25°C. A cyclohexane solution in which mol) was dissolved was added dropwise, and the mixture was stirred and reacted at the same temperature for 40 minutes. Next, after injecting 148 g of N,N,N',N'-tetramethylethylenediamine, 542 g of an n-hexane solution of n-butyllithium was added dropwise at -5 to 0°C, and the mixture was further heated to room temperature and reacted for 24 hours. Next, 245 g of 1-chloromethylnaphthalene was added to this reaction solution at 0 to 5°C.
The reaction and post-treatment were carried out in the same manner as in Reference Example 2 to obtain 200 g of a yellow oil. Add this to the column!
[Silica gel: Wakogel C-200, eluent: n-hexane/benzene = 1/4 (v/v)] Shi, 1
．． 71 g of 7-di(l-naphthyl)-3,5-heptanedione was obtained as a yellow oil. 'HNMRδppm (CDCI3): 2.56 (
4H,t,J・8Hz, -Cl{■CjlCO-X
2). 3.24(4N,t,J-8HZ,-(4C
}l2(:0-X 2) ,3.33(2H.s,-(
:0(Jx(:0-:Keto type 1/7), 5.27 (
I}l, s, -C-CH-GO-: c. Knoll type 6
/7), 7.17 ~7.19 (f4H, m, car aromatic ring x2), 15.43 (1}1, bs.-OH
(enol)). IR (Neat): 1720cm-', 1600
ca+-' Example 7.1.7-bis(4-chlorosulfonyl-1-naphthyl)-4-diazo3.5-heptanedione (in the general formula [IV], l -'l''-H
, X-X'-50■0. Synthesis of m−n*2 compound〉{l}4-diazo1,7-di(1-naphthyl)-3
．． Synthetic poison of 5-heptanedione 1.7-di(l-naphthyl) obtained in Example 3 -3.
30 g (791 mmol) of 5-heptanedione was dissolved in methylene chloride]60-, and 6.7 mg (791 mmol) of 5-heptanedione was dissolved in methylene chloride.
After adding 9 mmol), the P obtained in Reference Example 1 was heated at 0 to 5 °C.
16.3 g (83 mmol) of toluenesulfonyl azide was added dropwise. Thereafter, the reaction and post-treatment were carried out in the same manner as in Example 1 (1) to obtain 35 g of an orange oily substance. This was separated by column separation [silica gel: Wakogel C-200, eluent: n-hexane/methylene chloride = 4/l → 2/I (
v/v) ] L/, 4-diazo 1,7-di(I-
22.7 g of (naphthyl)-3,5-heptanedione were obtained as a pale yellow viscous oil. 'HNMRδGll)II((:D(13):3
．． 14 (4H, t, J・8Hx, -C}12C#L
(:0-X2). 3.42 (4H, Jin, J-8Hz
, -C%CH. GO-x 2nd daughter, 7.34-8.03
(14H, m, aromatic ring x 2). IR (Neat): 2120CI+-' (CN2
)． 1650cm-' ((:・0). (21 1 . 7-bis(4-chlorosulfonyl-1
-naphthyl)-4-diazo3,5-heptanedione (
In general formula [IV], z-Z'-H, X-X'・-
So2C! ．． Synthesis of compounds with m = n -2) Chlorsulfonic acid 25. A chloroform solution in which 1.0 g (27 mmol) of 4-diazo 1.7-di(1-naphthyl)-3.5-hebutanedione I obtained in (1) was dissolved in Og was added dropwise at 0 to 5°C. Below, (2) of Example 1
), the reaction and post-treatment were carried out in the same manner as described above to obtain crude brown oil 1.
5g was obtained. This was divided into column fraction rI1 [silica gel: Wakogel C-200, eluent: n-hexane/methylene chloride-1,/i-+ 1/4→1/9 (v/v)] L
/, 1,7-bis(4-chlorosulfonyl-1-naphthyl)-4-diazo 2.6 g of 3,5-hebutanedione was obtained as a pale yellow viscous oil. l HNMRδppm (CDα3): :l. 22
(4H,t,-CI12C!l!.(:0-X2),
:1.55(4H, t, -tJ, CH2CO-
2), 7.52 (2H, d, J4Hz, napht
hyl-C2X2), 7.71-7.88 (4N,
m, naphthyl-C, , c, X 2),
8.20 (2H, d, J=8Hz, na
phthyl-C8x2), 8.29 (2M, d
, J・8Hz, naphthyl-C3X2), 8.
85 (28, d, J・8Hx, naphthyl-C5
X2). IR (Neat): 2100cm-' ((JJ2
)． 1645 cm-' (11:・O). 11V(C}I3ON) λwax (ε): 23
9.4ni (65090). Elemental analysis value (C27H2.α2N206S2) theoretical value:
C%, 53.74. }I! k, 3.34. N turtle, 4.64 Actual value: C%, 53.59. H%
．． 3.51. N! Ii, 4.52, Example 8.1
．． 7-bis(4-methoxysulfonyl-1-naphthyl)
-4-diazo3,5-hebutanedione (general formula [IV
] Ni, l −'LM{, xmx'婁-so3c}
1,7-bis(4-chlorosulfonyl-1-naphthyl)-4-diazo3.5-heptanedione obtained in Example 7 (2). Og (6.6 mmol) in methanol 3
0ml? and 50-methylene chloride in a solution dissolved in 50-
1980 1 g of triethylamine was added dropwise at ~1O<0>C, and the reaction and post-treatment were carried out in the same manner as in Example 2 to obtain 3.7 g of a crude oil. This is separated by column [silica gel:
Wakogel C-200, eluent: n-hexane/ethyl acetate-5/l-+ 2/1 (v/v)] L, 1.
7-bis(4-methoxysul-2-1-naphthyl)-
1.9 g of 4-diazo 3.5-heptanedione was obtained as a white impure product. 'HNMRδppm (CDα3): 3.20 (
4H,t,-11:ICO-X2), 3.51(4H
, t. Ar-CHL-x2), 3.72 (611,
S, So, OH. x2), 7.49 (2N, d, J・
8Hz, naphthyl-C, x2). 7.64
~7.74(4H,m,naphthyl-(:e,h
x 2), 8.15 (2N, dd, J-8Hz and J-2Hz, naphthyl-CaX2), 8
．． 21 (2H, d, J・8Hx.naphthyl-1
:, x2), 8.65 (2H, dd, J・8Hz and J-2Hz, naphthyl-Csx 2). I
R(κBr5): 2120cm-'(-CN2), 1
640 cr! 1-'(C-0), U■((?}f3CN
)λmax (ε): 228.8r+n+(10
1940), Reference Example 4.1.7-G(2-naphthyl)
-3. Synthesis of 5-hebutanethione (l) Synthesis of ethyl 2-naphthoate 21 g (0.7 mol) of 2-naphthoic acid was dissolved in chloroform l. 5J2 and N,N-jethylformamide IO
After 167 g of thionyl chloride was added dropwise to the mixture under reflux, the mixture was stirred and reacted for 1 hour under reflux. After ts condensation of the reaction solution, the residue was diluted with triethylamine 1 at 10"C or less.
0.6 g and 150 g of ethanol. After stirring the reaction for another 1 hour at room temperature, 1°C of water was poured into the mixture.
The organic layer was separated by chloroform extraction. The organic layer was washed with water and then dried with anhydrous Mgso4. The desiccant was separated off, the solvent was distilled off, and the residue was distilled under reduced pressure to give bp. 145-147℃/2m
2 g of ethyl 2-naphthoate II of the mH) fraction was obtained as a colorless oil. This product crystallized after being left to cool. mp.
35.0-36.5°C. (2) Synthesis of 2-naphthalenemethanol Under a nitrogen atmosphere, 19 g of lithium aluminum hydride was added and suspended in 500 g of ethyl ether, and to this was added 11 g (0.55 mol) of ethyl 2-naphthoate obtained in step 11. The dissolved ethyl ether solution was added dropwise at below 10°C, and the reaction was further stirred at room temperature for 1 hour. After the reaction, 200% of ethyl acetate was added dropwise to deactivate the reducing agent, and then the reaction solution was added with 200% of concentrated hydrochloric acid and 20% of concentrated hydrochloric acid. The organic layer was left to stand and separated, and the obtained organic layer was washed with water, dried (anhydrous MgSO4), and the solvent was distilled off. 0 g was obtained as white crystals. mp. 8
0.5-81.5°C. (3) Synthesis of 2-chloromethylnaphthalene 53.7 g (0.34 mol) of 2-naphthalene methanol obtained in (2)
was dissolved in 300° C. of methylene chloride, and 60.7 g of thionyl chloride was added dropwise at 30±5° C., followed by reaction under stirring and reflux for 1 hour. After cooling, the reaction solution was washed twice with water, and anhydrous Mg
After drying with S04 and concentrating, 54 g of the residual oil was distilled under reduced pressure to bp. ! 44.2 g of 2-chloromethylnaphthalene in the 29-133°C/2 rnrnHg fraction was obtained as a pale yellow oil. This product crystallized after being left to cool. mp. 4
6.8-48.0°C. (4) Synthesis of 1,7-di(2-naphthyl)-3,5-hebutanedione 60% sodium hydride in 55% cyclohexane 46%
10.g of 2.4-hebutanedione was charged at 20-25°C. A cyclohexane solution in which Og (0.1 mol) was dissolved was added dropwise, and the mixture was stirred and reacted at the same temperature for 40 minutes. Next, after injecting 24.8 g of N,N,N',N'-tetramethylethylenediamine, 91 g of n-hexane solution of n-butyllithium was added dropwise at -5 to 0°C, and the temperature was further raised to room temperature and reacted for 24 hours. Ta. This reaction solution was then heated to 0-5°C.
35.3 g of 2-chloromethylnaphthalene obtained in (3)
was added dropwise, and the reaction and post-treatment were carried out in the same manner as in Reference Example 2 to obtain 32 g of a yellow oil. Column fraction ra [Silica gel C-
200, eluent: benzene] and 1.7-di(2-
15.4g of naphthyl)-3.5-hebutanedione is pale yellow? Obtained as crystal. ! Op. 123.0-125.0℃
. 'HNMRδpDffl(CDCt3): 2.6
5 (4H, t, J-8112, -CjJCO-
X 2), 3.08 (4H.t, J-8HZ, -CH
CII2C:O-X 2), 3.53(2H,s,-C
OC! l! ．． GO-: Keto type 3/5), 5.45 (
LH, s, -c=ch-co-:z nord type 2/5)
, 7.29 (2N, d, J-6.511z, 1-naphthyl-(. x 2) , 7.31 ~
7.40(4}1,m,naphthyl-C,,Ct
x2), 7.50 (21, bs, naphthyl-
C, x2), 7.73~'/. 8L (6H, rx
, napthy1-C3, C. ．． CaX
2), 15.46 (IH, bs, OH (enol))
．． ．． It{(KBrff): 1600cm-
'((:-0). Example 9.1.7-Bis(6-1 and 8-chlorosulfonyl-2-naphthyl)-4-diazo3.5-hebutanedione (general formula [IV] I.: , l-1”-H,X-
Synthesis of (l) 4-diazo 1,7-di(2-naphthyl)-3
．． Synthesis of 5-hebutanedione 1,7-di(2-naphthyl) obtained in Reference Example 4 (4)
6.85 g (18 mmol) of -3,5-hebutanedione was dissolved in 36 mg of methylene chloride, and 153 g of viveridine was added.
After adding 0 mg (18 mmol), the sample obtained in Reference Example 1 was heated at 0 to 5°C. p-Toluenesulfonazide 3.72g
(19 mmol) was added dropwise. The reaction and post-treatment were carried out in the same manner as in Example 1 (11), and a red viscous oil was obtained.
8g was obtained. This was separated by column separation [silica gel: Wakogel G-200, eluent: n-hexane/methylene chloride =
1/1 (V/V)IL/, 4-diazo1.7-
Di(2-naphthyl)-3,5-heptanedione 6.8
g was obtained as a yellow viscous oil. 'HNMRδppm ((41CfLs): 3.1
2 (8H, bs, -(:JIJj, CO-x2),
7.33 (2}1, d, J・8Hz, naphthy
l-(;4X2), 7.41-7.62(4H, m,
naphthyl-C5. C7X2). 7.64 (
2H, bs, naphLhyl-C+ X2), 7.
75 ~7.81 (6H, IIl, naphthyl
C,. C6, C6X 2). IR (Neat): 2100co+-'(-(:N
2), 1650cm-'(C■0),12) 1,
7-bis(6-1 and 8-chlorosulfonyl-2-naphthyl)-4-diazo3,5-hebutanedione (general formula [
IV]! ．． : at, l-1"-H, X-X'-SO2C
l. Synthesis of compound m-n-2) In 14.7 g of chlorosulfonic acid, 6.4 g (15.7 A chloroform solution in which 1 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 (2) of Example 1 to obtain 1.1 g of a yellow oil. This was divided into column fraction M [silica gel: Wakogel C-200, eluent: n-hexane/methylene chloride = 1/2 (v/v) It,, 1,7-bis(6- and 8-chlorosulfonyl-2- naphthyl)−
4-diazo 3.5-hebutanedione (1:1 mixture)
250B was obtained as a slightly yellow viscous oil. 'HNMRδppln((:D(f3): 3.1
9 ~3.31 (8H.m, -C!LICjX-X
2), 7.52-8.36 (8H, lI1, aromatic ring x
2), 8.54 (2H, bs, naphthyl-C
,X 2:6-SOzGl isomer]/2) ,8.71
(2H, d, J・911z, naphthyl-C7x
2:8-SO2Cl isomer 1/2) ,, JR(Neat): 2110cm-'(-CNz)
．． 1650c ``'(C・O). Elemental analysis value (C27H2.02N206S2) theoretical value:
C$, 53.73; }1%, 3.34: N! k
, 4.64 Actual value: C zero, 53.49. H! k,
3.45. N turtle, 4.81,? Example 5. Synthesis of 1.7-bis(4-chlorophenyl)-3,5-hebutanedione Cyclohexane 110m7! 9.2 g of 60% sodium hydride was added to the 2,4-
A cyclohexane solution in which 20.0 g (0.2 mol) of benzanedione was dissolved was added dropwise, and the mixture was stirred and reacted at the same temperature for 40 minutes. Next, after injecting 49.6 g of N,N,N',N'-tetramethylethylenediamine, the n-
182 g of a n-hexane solution of butyl lithium was added dropwise, and the temperature was further raised to room temperature and reacted for 24 hours. Next, 74.7 g of 4-chlorobenzyl chloride was added dropwise to this reaction solution at 0 to 5° C., and the reaction was then subjected to post-treatment in the same manner as in Reference Example 2 to obtain 69 g of red-orange semi-molten crystals. This was recrystallized from methanol and 1,7-bis(4-chlorophenyl)'
- 24.7 g of 3.5-hebutanedione was obtained as white prism crystals. Death... 74.6-76. lt:. 'HNMRδI)pIn((:D(13): 2.
55 (411,t,J■7.3Hz,Ar-CH2(
:Ll(:0-X2), 2.88(4H,t,J-
7.3}12,Ar-CH,-X2). 3.51 (
211,s, -COCizCO-: Keto type 3/20)
, 5.37 (1}1,s, -C-C}j-CO-: enol type 17/20), 7.07-7.11 (411,
■ ? , phenyl-C2, C6x2), 7.23x7
．． 26 (4H, m, phenyl-C3, CF, X
2) , 15.35 (IH,s,-Off(e
nol)). rR (KBr tablet): 3300cm-', 1640
cm-' ((:■0), 1600C!I+-'Example 10. 1,7-bis(4-chloro-3-chlorosulfonylphenyl)-4-diazo-3,5-heptanedione (general formula [■1 In , Y-Y'-(!, X-X
Synthesis of '-So2 (; I, m = n-2 compound) (11 Synthesis of 1.7-bis(4-chlorophenyl)-4-diazo3.5-hebutanedione 1. Obtained in Reference Example 5. 7-bis(4-chlorophenyl)-
3.5-Hebutanedione 12. Og (34.4 mmol) was dissolved in 70-methylene chloride and biperidine 2.9-
g + 34.4 mmol), and then 7.1 g (36
mmol) was added dropwise. Thereafter, the reaction and post-treatment were carried out in the same manner as in Example 1 (1) to obtain 15 g of an oily substance. This was applied to column 11 [Silica gel: Wakogel C-200,
Eluent: methylene chloride 1, 1,7-bis(4-chlorophenyl)-4-diazo, 3,5-hebutanedione 1
．． 2 g was obtained as pale yellow crystals. ? p. 8: 3°C (decomposition). 'HNMRδI)l)ffi((:DCt3): 2
．． 93 ~3.01 (8N, m, Ar-%CHIGo-
x2). 7.12 ~7.16 (4H.m, phen
yl-C2, C6x2), 7.24 ~ 7.27 (4
H, m, phenyl-C3, G5x2). IR (κBri7): 2100cm-'(-CN2),
1650cm-'(C・0), UV((Jl3CN)
λwrax (ε): 225. Onm (315
50). +21 1.7-bis(4-chloro-3-chlorosulfonylphenyl)-4-diazo3.5-hebutanedione (in general formula [■1, Y-Y'-Cl .X-X'
Synthesis of 1.7-bis(4-chlorophenyl)-4-diazo-3.5-heptanedione obtained in (1) in 9.9 g of chlorosulfonic acid A chloroform solution in which 3.98 g (10.6 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 (2) of Example 1 to obtain 1.3 g of crude oil. This was subjected to column fraction 1!1 [silica gel: Wako Gel C-200, eluent: methylene chloride] and converted to 1,7-bis(4-chloro-3-chlorosulfonylphenyl)-4-diazo3.5- Butanedione l.1
g was obtained as a pale yellow viscous oil. 'HNMR δppm (CDcL): 3.08
(8tl,s, -C%-x books), 7.55 (4H,s,
phenyl-CB, (:6X2), 7.99 (2H
, s, phenyl-G2X2). JR (Neat): 2110CI! 1-'(-(;
N2), 1655cr' (CJ). UV (CH3
ON) λ old × (ε): 227. Onm(3414
0). 287.0 nm (5640). Elemental analysis value (C+sH+4CI.4NzOsS2) Theoretical value: (J, 39.88. HX, 2.47: N
! k, 4.90 Actual value: C! Ii, 40.09;
H turtle. 2.31; N%;, 4.82, Reference example 6
．． 1. Synthesis of 7-bis(4-methoxyphenyl)-3,5-hebutanedione 60% sodium hydride in 200 parts of cyclohexane
A cyclohexane solution in which 37.3 g (0.37 mol) of 2.4-bentanedione was dissolved was added dropwise at 20 to 25° C., 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 n-hexane solution of n-butyllithium was added dropwise at -5 to 0°C, and the temperature was further raised to room temperature and reacted for 24 hours. Ta. Then add 0 to this reaction solution.
133 g of 4-methoxybenzyl chloride at ~5°C? The reaction and post-treatment were carried out in the same manner as in Reference Example 2.
Crude crystals were obtained. This was recrystallized from ethanol and 1.
95.1 g of 7-bis(4-methoxyphenyl)-:l,5-heptanedione was obtained as pale yellow short needles. mp
．． 73.5-7642°C. 'HNMRδPPffi (CDl:13): 2.
54 (4N, t, J・8Hz, Ar-CH2c6co-
x2), 2.86(4Lt, J・811z, ^r-(
:jj,-x 2) ,3.78(8H,s,-(;i
j, 10-X 2) , 5.41 (IH, s, -C-
(Jj-GO-: 1 enol type 10/10), 6.82 (4}!, d, J
・9Hz, phenyl-1. , c, x2), 7.0
9 (4H, d, Js9}IZ. phenyl-C3,
C,, X2), 15.43<IH, bs, -OH). IR (KBrvE): 1600cm-' (C:-
C). Example 11 1,7-bis(3-chlorosulfonyl-4
(1-methoxyphenyl)-4-diazo-3,5-hebutanedione ('l'-Y'-0(;
}I3,X-X'--SO■α, m=n=2 compound)
Synthesis fl3 Synthesis of 1,7-bis(4-methoxyphenyl)-4-diazo-3,5-heptanedione 1,7-bis(4-methoxyphenyl)-3 obtained in Reference Example 6
．． 4.5 g (13.2 mmol) of 5-hebutanedione was dissolved in 26 mmol of methylene chloride, and 1.5 g (13.2 mmol) of 5-hebutanedione was dissolved in 1. ．． lmg
After adding (13.2 mmol), 2.73 g (13
．． 9 mmol> was added dropwise. The reaction and post-treatment were carried out in the same manner as in Example 1 (1), and 5.6 g of dark brown oil was obtained.
I got it. This was separated by column [silica gel: Wako gel G]
-200, eluent: methylene chloride, 1,7-bis(
2.4 g of 4-methoxyphenyl)-4-diazo-3.5-hebutanedione were obtained as a yellow viscous oil. 'HNMRδppm ((DCt3): 2.87~3
．． 03 (8ft, m, -1:H, -x4), 3.7
8 (6H,s, (:JO-x2), 6.82 (4
8, d, J・8.6Hz, phenyl-C,,C. X
2), 7.13 (4H, d, J・8.6Hz, phe
nyl-G2, G6X 2). JR (Neat): 2900cm", 2100cm-
'(-CN2), 1650cm-'(C・0). (2) 1,7-bis(3-chlorosulfonyl-4-
methoxyphenyl)-4-diazo-3,5-hebutanedione (general formula [II], Y-Y'-0(:H3,
X-X'--SO2Ci. Synthesis of compound m-n・2) k in 5.6 g of Kulsul*nllIe: (1) 114
Ta f. 7-His-(4-methoxyphenyl)-4-diazo 3.5-hebutanedione 2.2 g (6 mmol)
A chloroform solution in which 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 Example 1 (2) to obtain 1.8 g of a crude product. This was separated by column separation [silica gel: Wakogel C-200, eluent: n-hexane/
Ethyl acetate = 1/1 (v/v)] 1,7-bis(3-chlorosulfonyl-4-methoxyphenyl)-4
-Diazole 1.7 g of 3,5-hebutanedione was obtained as pale yellow powder crystals. mp. 51.0-52.0°C. 'tlNMR l3ppm (CDα3): 2.99
~3.05 (8tl,m,-(:%-X 4) ,4
．． 03 (6tl,s, (Jl,0-X 2) , 7
．． 06 (28, d, J・8.8Hz, phenyl<
,X2), 7.57(2H, dd, J・8.8Hz,
and J-2.2Hz, phenyl 10. x2),
7.79 (2H.d.J-2.2flz, pheny
l-(:2x2). IR (KBr tablet): 2100eam-'(-CN2). 1650cr' (C・0). ! JV (CH, CN) λwax (ε) +228. O
n! ! +(35000) ,306.0nrB(755
0). Elemental analysis value (C21H2.Cft2N20sS2) Theoretical value: C96.44.77; H96,3.58
．． Nk, 4.97 Actual value: (J, 44.80;
H51;, 3.51; N%, 5.07, Application example 1, 1.7-bis(3-chlorosulfonyl-
4-methylphenyl)-4-diazo 3.5-hebutanedione I. 5g and para-cresol novolac resin (
A photosensitive material A was obtained by stirring and dissolving 8.5 g of diethylene glycol dimethyl ether (molecular weight: 10,000) in 20 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 in step 7 was spin-coated onto a substrate 1 made of a semiconductor or the like, and prebaterized on a hot plate at 90 DEG C. for 2 minutes to obtain a photosensitive material film 2 having a thickness of 1.2 mm. (Figure 1(a)). Note that an insulating film, a conductive film, etc. are often formed on the substrate 1. Next, 248.4nm
was selectively exposed to the excimer laser 4 through a mask 5. (Figure 1(b)). And finally, NMD-3 (
The exposed portion of the photosensitive material film 2 was dissolved and removed by developing for 60 seconds with a resin pattern (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to obtain a resin pattern 2a. (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 less. The surface of the substrate 1 was etched using this pattern 2a as an etching mask. FIG. 2 shows ultraviolet spectroscopy of this film 2 as a resist material. In FIG. 2, the solid line (1) shows the results before exposure, and the broken line (---) shows the results after exposure. As is clear from this result, the change in transmittance before and after exposure at 248.4 nm was a large value of about 74%, indicating that this photosensitive material and the photosensitive compound of the present invention showed good reactivity to KrF excimer laser. I understand that. Application example 2. 1,7-bis(3-chlorosulfonyl-) obtained in Example 1
4-Methylphenyl)-4-diazo 3.5-hebutanedione I. 5g and metacresol novolak resin (
A photosensitive material was obtained by stirring and dissolving 8.5 g of ethyl cellosolve acetate (with a molecular weight of 20,000) in 20 g of ethyl cellosolve acetate. Using this, ultraviolet spectroscopy measurements of batanine formation skin were carried out in the same manner as in Application Example 1, and good results almost equivalent to those in Application Example 1 were obtained. Application example 3. 1,7-bis(4-chlorosulfonyl=
A photosensitive material was obtained by stirring and dissolving 1.5 g of 1-naphthyl)-4-diazo3.5-hebutanedione and 8.5 g of para-cresol novolac resin (molecular weight: 10,000) in 20 g of diethylene glycol dimethyl ether. Using this, pattern formation and ultraviolet spectroscopy measurements were performed in the same manner as in Application Example 1, and good results almost equivalent to those in Application Example 1 were obtained. Application example 4. 1.5 g of 1.7-bis(4-chloro-3-chlorosulfonylphenyl)-4-diazo-3.5-heptanedione obtained in Example IO and meta-cresol novolak resin (
A photosensitive material was obtained by stirring and dissolving 8.5 g of ethyl cellosolve acetate (with a molecular weight of 20,000) in 20 g of ethyl cellosolve acetate. Using this, pattern formation and ultraviolet spectroscopy measurements were performed in the same manner as in Application Example 1, and good results almost equivalent to those in Application Example 1 were obtained. Note that the resin in the photosensitive material is required to be highly transparent to far ultraviolet light such as 248.4 nm in order to reduce surface absorption of light in the photosensitive material. Similar good results can be obtained by using styrene resin, maleimide resin, hydroxystyrene resin, orthochlorometacresol/novolak resin as resins other than those used in Application Examples 1 to 4, but of course the invention is limited to these. Not that it will be done. Regarding the solvent, any solvent may be used as long as it can dissolve the resin and the photoreceptor. In this example, ethyl cellosolve acetate and diethylene glycol dimethyl ether were used, but the solvent is not limited to these. Application Examples 5 to 16 The compounds of the present invention obtained in each example were used as photosensitizers, and poly(paravinylphenol) resin (molecules 17,0
00), a photosensitive material was obtained using diethylene glycol dimethyl ether as a solvent. These photosensitive materials were spin-coated onto a semiconductor substrate and prebaked to prepare a photosensitive material sample with a film thickness of 1.0-. The dissolution rate in aqueous solution was measured. Further, a pattern was formed using the above photosensitive material in the same manner as in Application Example 1. The results are shown in Table 1. As is clear from the results shown in J's Lower Margin Table 1, good patterns were obtained with each photosensitive material. In addition, the dissolution rate of the films made with each photosensitive material was 150 nm/min or less, and the dissolution rate of the film made similarly using only poly(barabinylphenol) resin (molecular weight 7,000) was (4,000 nm/min).
A very good value was obtained compared to OOr+m/min). 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. In addition, in Application Examples 5 to 16, styrene resin, pidroxystyrene resin, baracresol/novolac resin, metacresol/novolac resin, orthochlorometacresol/novolac resin, etc. Approximately the same results can be obtained by using 1 (/). Application Example 17 A contrast 1/enhanced material for pattern formation consisting of the following composition was prepared: 1.7-bis(3-chlorosulfonyl-4-methylphenyl) -4-diazo3.5-hebutanedione 4.
Og Balak I Nosol Novolac Resin (Molecular Weight 5,000) 2.5
g Ethyl cellosolve acetate 20.0 g The pattern-forming contrast-enhancing material thus prepared has a thickness of 0 when used as a pattern-forming organic film.
．． Before exposure with a κRF excimer laser of 248.4 nm at 12 μ■ {the difference in transmittance at 248.4 nm is over 70%, which is very high, and it works to improve the contrast of the incident light. Understood. FIG. 3 shows the resist 1 pattern formation and lithography process using the pattern-forming contrast-enhancing material according to the present invention. A body resist 3 (MP2400
: Sibley Co., Ltd.) to a thickness of 1.5 μm (see Figure 3 (
a)). Next, a water-soluble organic film 6, such as a mixed solution of pullulan and polyvinylpyrrolidone, is applied and formed on the photoresist 3. At this time, the mixing weight ratio of bullulan and polyvinylpyrrolidone was 4:1, and the film thickness at this time was approximately 0.1 to 0.3 pJ so as not to affect pattern formation. Note that this water-soluble organic film as an 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 mm. Here, the lower resist layer, the intermediate water-soluble organic film, and the water-soluble organic film and the single-layer pattern-forming organic film were laminated with excellent adhesion. Then, reduction projection exposure method (5:1 reduction, N8 = O
248.4 nm selectively through mask 5 by J6)
Expose the KrF 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, and at the same time, the lower resist 3 is developed to form a resist pattern 3b. Figure 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 of 90 degrees). In addition, 1,7-bis(3-chlorochloride-4-menalphenyl)-4-diazo3.
Substantially the same results can be obtained even when the compounds of the present invention obtained in Examples 2 to 1l are used as photosensitizers in place of 5-hebutanedione. [Effects of the Invention] The present invention provides a novel photosensitive compound having excellent reactivity to, for example, a 248.4 nm excimer laser, and provides a photosensitive material using the photosensitive compound according to the present invention. For example, κrF excimer laser (248.4
When applied to deep UV (nm) exposure resists and contrast-enhancing materials, fine patterns with good shapes on the submicron order can be easily obtained. It is of great value for formation.

[Brief explanation of drawings]

FIG. 1 is a process cross-sectional view of a pattern forming method of Application Example 1 using a photosensitive material containing the compound of the present invention, and FIG. 2 is a 248.degree.
Ultraviolet spectral characteristics near 4 nm (solid line is before exposure, broken line is after exposure), FIG. 3 is a process cross-sectional view of the pattern forming method of Application Example 17, and FIG.
0), and Figure 5 is an ultraviolet spectral characteristic diagram near 248.4n of MP2400 (
However, the solid line is before exposure, and the broken line is after exposure). 1. One substrate, 2... Photosensitive material film for pattern formation, 3.
-Positive resist, 4=KrF excimer laser, 5.1 mask, 2a, 3a, 3b=resin pattern, 6.1 water-soluble organic film, 7-contrast enhancement material film for pattern formation

Claims (4)

[Claims] (1) General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] [In the formula, R^1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ represents {however,
X is a hydrogen atom, -SO_2Cl, -SO_2Br, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_3H or -S
O_3R^5 (However, R^3 and R^4 each independently represent a hydrogen atom or an alkyl group that may have a substituent, or R^3, R^4 and N They may form a ring such as a piperazine ring, piperidine ring, pyrrolidine ring or morpholine ring, and R^5 represents an alkyl group. Also, -SO_2Cl, -SO_2Br and -
SO_3H includes its quaternary salt. ), Y is a hydrogen atom,
represents an alkyl group, an alkoxy group or a halogen atom,
Z represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. }, R^2 represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {However, X' is a hydrogen atom, -SO_2Cl, -SO_
2Br, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_
Represents 3H or -SO_3R^8 (However, R^6, R
^7 each independently represents a hydrogen atom or an alkyl group which may have a substituent, or R^6, R^7 and N
and may form a ring such as a piperazine ring, piperidine ring, pyrrolidine ring or morpholine ring, and R^8 represents an alkyl group. Also, -SO_2Cl, -SO_
2Br and -SO_3H include their quaternary salts. ), Y
' represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and Z' represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. }, m and n are 1-2
Represents an integer of 0 (except when Y and Y' are both hydrogen atoms). ] A compound represented by. (2) The compound represented by the general formula [I] has the general formula [II] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, X, X', Y, Y', m and n are the same as above. ) The compound according to claim (1), which is a compound represented by: (3) The compound represented by the general formula [I] has the general formula [III] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [III] (In the formula, X, X', Y, Z', m and n are the same as above. ) The compound according to claim (1), which is a compound represented by: (4) The compound represented by the general formula [I] has the general formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X, X', The compound according to claim 1, wherein Z, Z', m and n are the same as defined above.