JPH03190873A - Halogenothiophene dioxide and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X<1> to X<3> are each halogen or H; Y is of formula II or OR<1> (R<1> and R<2> are each H or hydrocarbon); Z is H or free bond in combination with X<3>]. EXAMPLE:3,3-Dichloro-2,3-dihydro-1,1-dioxythiophen-4-yl N,N- diethyldithiocarbamate. USE:An antifoulant. Having high controlling effect on algae, microorganisms, aquatic organisms, etc., for a long period and antifouling effect on underwater structures. PREPARATION:The objective compound of the formula I can be obtained by reaction between a compound of formula III (R<4> is halogen), a second compound of formula IV and its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to a novel formula [wherein XI and X2 are the same or different, -O
R' (wherein R1 and R2 are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent)
A compound represented by the formula or OR' (where R1 and R2 are the same or different and have a hydrogen atom or a substituent, The present invention relates to halogenothiophene dioxides represented by 1, in which Z represents a hydrogen atom or a bond together with X3, and a method for producing the same.

Prior Art A thiophene-1,1-dioxide compound represented by the following formula (II) [wherein Xo represents a halogen atom or a hydrogen atom] is described in U.S. Pat. No. 2,957,887, and is It is already known as an active ingredient in stain paints. Also, the following formula (
III) 2R' [In the formula, M represents an alkali metal atom or an ammonium group, and R' and R// represent an alkyl group, a cycloalkyl group, a phenyl group, an argylaryl group, or a hydrogen atom. It is produced in large quantities as a rubber vulcanizing agent, polymerization inhibitor, and agricultural fungicide. However, the halogenothiophene dioxides represented by (I) have not been synthesized and their uses are unknown.

Problems to be Solved by the Invention In oceans, rivers, lakes, etc., there are many aquatic creatures such as Fujitbo, sea squirt, Serpura, Murasaki mussel, Japanese snail, Thrush bug, Blue laver, Ulva, etc. When an underwater structure (described in detail below) is installed or put into service, aquatic organisms grow attached to the surface of the submerged area from the spray, causing various damage. For example, when aquatic organisms adhere to the hull of a ship, the frictional resistance with water increases, resulting in a decrease in sailing speed, and in order to maintain a constant speed, fuel consumption increases, which is economically undesirable. Furthermore, if aquatic organisms adhere to port facilities that are fixed underwater or on the water surface, it becomes difficult for these organisms to fully perform their individual functions, and moreover, they may erode the base material. Furthermore, if it adheres to aquaculture nets or fixed nets, the nets may become clogged and the fish may be killed.

Conventional antifouling methods mainly involve painting with antifouling paint containing highly toxic antifouling agents such as organic tin compounds and cuprous oxide.
This was done by gradually dissolving the antifouling agent from the paint film into water, and the adhesion and growth of aquatic organisms was almost completely prevented.

However, since these antifouling agents are highly toxic, they are unfavorable in terms of environmental safety and hygiene for workers during the production and painting of the paint, and the antifouling agents that elute into the water may remain as they are, so they may not last long. From a practical standpoint, there is a risk of contaminating water bodies, and it is also expected that it will accumulate in the bodies of fish and shellfish, causing negative effects. In addition, the above compounds (I[) and (II
I) is suitable as a control agent against microorganisms, algae, living organisms, etc. in water because it causes skin irritation and is difficult to handle, and because it is highly soluble in water, it flows out (reduces activity). It's not a thing.

Based on this situation, there is a strong desire to develop a low-toxicity antifouling paint (composition) that has excellent antifouling properties over a long period of time and is extremely safe for the human body and seafood. Ta.

Means for Solving the Problems The present inventors have developed a compound that has no or very low skin irritation and oral toxicity, has no difficulty in handling, and has an excellent control action against microorganisms, algae, aquatic organisms, etc. Various studies were conducted to find out.

As a result, a compound represented by the formula [wherein Xl, X2, and X3 have the same meanings as above, and X' represents a halogen atom] and the formula % formula % () 1 where Y has the same meaning as above. When a compound represented by the formula or a salt thereof is reacted with a compound represented by the formula [wherein Xl, X2 and Y have the same meanings as above] and a hydrogen halide, a novel We found that halogenothiophene dioxides (I) can be obtained, and that the obtained compound (I) unexpectedly has superior properties as a control agent against microorganisms, algae, aquatic organisms, etc. Based on these findings, the present invention was completed. That is, the present invention provides (1) halogenothiophene dioxides (I), (2)
A method for producing compound (1), characterized by reacting compound (IV) and compound (V) or a salt thereof; (3) a method for producing compound (1), characterized by reacting compound (VI) and hydrogen halide; The present invention relates to a method for producing a compound represented by the formula contained in compound (1), where Xl, X2, X4 and Y have the same meanings as above.

In the above formula, Xl, X2, and X3 are the same or different and represent a halogen atom or a hydrogen atom; roughly, X3 represents a bond together with Z; and X4 represents a halogen atom. These Xl,
The halogen atoms represented by X2, X3 and X4 are:
For example, CQ, F, Br, etc. are used. A preferred such halogen atom is CQ.

R1 and R2 are the same or different and represent a hydrocarbon group which may have a hydrogen atom or a substituent. Examples of the hydrocarbon group represented by R1 and R2 include methyl, ethyl, n-propyl, i-propyl, n-butyl, 1-butyl, t-butyl, n-pentyl, and 1-pentyl.

Straight chain or branched C1-6 alkyl group such as n-hexyl,
C2-4 alkenyl groups such as vinyl and allyl, ethynyl,
02-4 fulkynyl group such as propynyl, C3-fi cycloalkyl group such as cyclopropyl, cyclobutyl, cyclohexyl, C8-6 such as cyclopropenyl, 1 or 2-cyclohexenyl, l,4-cyclohexagenyl, etc.
Cycloalkenyl group, C6-10 aryl group such as tolyl, naphthyl, benzyl, phenethyl, etc.
A 7-1o aralkyl group or the like is used. These hydrocarbon groups may have one to three substituents, and examples of such substituents include a hydroxyl group, a halogen atom (C
I2.8r, etc.), C1-4 alkoxy (for example, methoxy, ethoxy, etc.), sulfo group, amino group, etc. are used,
The hydrocarbon group is 03-, cycloalkyl group, C36 cycloalkenyl group, C, , aryl group, C7. When it is an aralkyl group, it may be further substituted with 1 to 4 01- or alkyl groups (eg, methyl, ethyl, n-propyl milpropyl, n-butyl, etc.). Preferred examples of Y include dimethylamino, diethylamino, di-1-propylamine, and di-1-propylamine.

Di-C1-, alkylamino groups such as di-n-butylamino, and the like are used. Z represents a hydrogen atom or a bond together with I3. Therefore, when Z is a hydrogen atom, compound (I) is a compound represented by the formula [wherein, Xl, I2, I3 and Y have the same meanings as above], where Z is If indicated, it can indicate a compound represented by the formula [wherein Xl, I2 and Y have the same meanings as above]1. It is preferable that 2 is a hydrogen atom.

Preferred examples of compound (I) include compounds represented by the formula [wherein, X represents a halogen atom and R represents a C3-4 alkyl group]. Expression (■ Tsuchu, X
represents, for example, a halogen atom such as C12, Br, F, etc., and preferably represents, for example, Ca. R is a linear C such as methyl, ethyl, n-propyl, n-butyl, etc.
Indicates a 1-4 alkyl group.

Compound (1), which is the object of the present application, and compound (Ib) contained in compound (I), (I) produces isomers at the asymmetric carbon atom, but not only isomers alone but also mixtures thereof are the object of the present application. The object (I) of the present application can be synthesized by reacting compound (IV) with compound (■) or a salt thereof.

Specific examples of the compound (IV) used include, for example, chlorothiophene dioxide (for example, 3,3°4,4-tetrachlorotetrahydrothiophene 1,1-dioxide, 3,3,4-1-lichlorotetrahydride). Thio-7ene-
1,1-dioxide, 3bromo-3,4,4-trichlorotetrahydrothiophene-1,1-dioxide, 3,
4-dichlorotetrahydrothiophene-1,I-dioxide, etc.). Compound (V) may be used in free form, but it is preferable to use it in the form of a salt, such as alkali metals (Na, etc.), alkaline earth metals (Ca, Mg, etc.).
), salts with amines (ammonia, methylamine, dimethylamine, diethylamine, triethylamine, etc.), etc. are often used. Specific examples of such salts of compound (V) are:
For example, alkyl dithiocarbamates (e.g. N
, N sodium dimethyldithiocarbamate, N,
Potassium N-diethyldithiocarbamate, Sodium N,N-isopropylcarbamate, Sodium N,N-dibutylcarbamate, Sodium N-ethyl N-7enyldithiocarbamate.

Sodium N-pentamethylenedithiocarbamate, 2-sodium ethylenebisdithiocarbamate, N-
ammonium methyldithiocarbamate, sodium N-2-hydroxyethyldithiocarbamate, etc.), and xanthates (e.g., sodium methylxanthate, sodium methylxanthate,
potassium butyl xanthanoate, cellulose xanthate, etc.).

This reaction is preferably carried out under conditions such that the compound represented by the formula [the symbols in the formula have the same meanings as above] will not be produced as a by-product, for example in a single solvent (homogeneous system) or in water. It is carried out at a relatively low temperature (-
10°C to 45°C), preferably below room temperature (0°C to 45°C)
It is best to carry out the reaction under mild conditions (at 30°C), and if the reaction is allowed to proceed under such conditions, the product of formula (I) can be obtained in good yield while suppressing the decomposition reaction of the raw materials and target substances. be able to. Examples of solvents suitable for homogeneous reactions include alcohols such as methanol and ethanol, N,
Amides such as N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, etc. are used. A good example of the heterogeneous reaction solvent is a solvent that can dissolve the compound (TV), such as ethyl acetate.

Acetic esters such as methyl acetate, hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, ethers such as tetrahydrofuran, and ketones such as methyl ethyl ketone are used. Catalysts (eg, platinum, palladium, platinum black, etc.) are usually not required, but conventional catalytic amounts may be used if desired.

In a homogeneous reaction, the reaction is rapidly promoted and generates heat, so it is preferable to carry out the reaction under cooling while suppressing the reaction temperature. In a heterogeneous reaction, since the oil is in a suspended state, the reaction occurs at the interface of the suspended oil droplets, the reaction temperature is mild, and the reaction is preferably carried out for a long time.

The reaction temperature is usually -30°C to 90°C, preferably 10°C.
It is more preferably 0°C to 30°C than 1°C to 45°C. The reaction time is usually 5 to 40 hours, preferably 15 to 40 hours.
It is 30 hours. The amount of raw materials (IV) and (V) to be used is 1 to 5 mol, preferably 1 to 1.5 mol, of compound (V) or a salt thereof per 1 mol of compound (IV).

Compound (I) thus obtained can be isolated and purified by known means such as concentration, solvent extraction, liquid conversion, distillation, fractional distillation, salting out, crystallization, recrystallization, chromatography and the like. In particular, when this reaction is carried out in a heterogeneous system using the salt of compound (V), there is no danger of fire because it is an aqueous system, and the salt, which is one of the by-products, is added to the aqueous layer to achieve the desired formation. Product (I) is dissolved in the oil layer, and the two can be easily selected and separated by two-layer separation (liquid separation operation), and the reaction is mild, so the yield is improved.

6- Furthermore, in the present invention, by reacting compound (VI) with hydrogen halide, a compound (Z is a hydrogen atom and X3 is a halogen atom), which is one of the objects of the present application (I), can be prepared (■°) can be obtained.

Examples of hydrogen halides used include HBr,
HCff, etc., and these are used in gaseous or aqueous solution. The amount of hydrogen halide used is 1 to 6 mol, preferably I-1.2 mol, per 1 mol of compound (■). The reaction is preferably carried out in a solvent, and examples of the solvent used include halogenated hydrocarbons such as carbon tetrachloride, chloroform, and dichloroethane, esters such as ethyl acetate, and sulfoxides such as dimethyl sulfoxide.

The reaction temperature is usually -10°0-150°C, preferably 60°C.
-120°C. The reaction time varies depending on the raw materials and solvent used, but is usually 1 to 40 hours, preferably 8 to 20 hours. under pressure, e.g. 1.5
The reaction can also be allowed to proceed under a pressure of ~3 atm. The thus obtained compound (1) was isolated by the above-mentioned known method.

Can be purified.

Among the raw material compounds used in the method for producing the target product (I), compound (IV) can be synthesized, for example, by the method described in Japanese Patent Publication No. 353517, Japanese Patent Application Publication No. 52-10263, etc., or a method analogous thereto, Compound (V) or a salt thereof is described, for example, in Pesticide Science, Vol. 23, pp. 93-102 (1988), J, A, C, S, 5.
It can be synthesized by the method described in Vol. 4, p. 1163 (1932) or by a method analogous thereto. Also,
Compound (Vl) can be obtained by the reaction of compound (IV) and compound (V) or a salt thereof in the method of the present invention.

The compound (1) obtained as described above has high biological activity, and is effective against microorganisms such as bacteria, molds, and yeasts, algae from freshwater and seawater, and aquatic organisms such as Fujitbo, sea squirt, Serpura, mussels, Japanese snails, and snails. Furthermore, it has the advantage of being stable and long-lasting in weakly alkaline water and seawater, and having low skin irritation and oral toxicity. Therefore, the target compound (I) is suitable for use in, for example, ships, port facilities, buoys, pipelines, bridges, submarine bases, submarine oil field drilling equipment, power plant conduit pipes, aquaculture nets, fixed nets, etc. (these are referred to as "underwater structures"). It can be used to produce a highly safe antifouling coating composition suitable for preventing aquatic organisms from adhering to and growing on the surface of the underwater structure. Here, "antifouling" refers to preventing aquatic organisms from growing on the surface of underwater structures.

The antifouling coating composition of the object (I) of the present invention can be produced according to a conventional method, and generally contains about 1 to 350 parts by weight of the object (I) per 100 parts by weight (solid content) of the paint resin.
Preferably about 5 to 150 parts by weight, more preferably about 5 parts by weight.
It is blended within the range of 80 parts by weight. The content ratio of the object (1) in the entire antifouling paint composition should not be limited as long as the purpose is achieved, but it is usually about 0.1 to 50 parts by weight per about 100 parts by weight of the composition. parts by weight, preferably about 0.5 to 25 parts by weight. The resins used for coatings can be divided into those that dissolve in water and those that hardly or do not dissolve in water.Paints using the former are called soluble matrix types, and the latter are called insoluble matrix types. The former and the latter can coexist. The antifouling coating composition of object (I) may be of any type.

The paint resin used as a vehicle in the antifouling paint composition of object (1) is one of the base components for forming an antifouling paint film, and is not used in conventional antifouling paints. For example, vinyl chloride-
Vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer, styrene-butadiene copolymer,
Chlorinated rubber resin, chlorinated polypropylene resin, petroleum resin, alkyd resin, acrylic resin, phenolic resin, synthetic rubber, epoxy resin, silicone rubber, silicone resin, Teflon resin, rosin resin, etc. used. Among these, the use of silicone rubber or silicone resin is particularly preferred in order to further improve the antifouling properties since the zero surface energy of the coating film can be reduced.

Furthermore, in the antifouling coating composition of object (I), in addition to the above components, a plasticizer may be further blended in order to adjust the physical properties of the antifouling coating film, such as a heptatalic acid derivative. (Dimethyl phthalate 1-, diethyl phthalate, dibutyl phthalate 1-, diisobutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, butyl glycolate, etc.); Phosphoric acid derivatives (tricresyl phosphate, triphenyl phosphate, diphenyl phthalate, etc.); ester phosphate, etc.); Epoxy derivatives (epoxy soybean oil, etc.): Paraffin and paraffin derivatives (
chlorinated paraffin, etc.) can be used. Such a plasticizer is preferably blended in an amount of 20 parts by weight or less per 100 parts by weight of the coating resin. Also, the object (
In the antifouling paint composition of I), sufficient antifouling effect is exhibited even when only the target substance (I) is used as the antifouling component;
If necessary, general antifouling agents that are blended in ordinary antifouling paints, such as organic tin compounds [triphenyltin hydroxide, triphenyltin chloride, triphenyltin fluoride, triphenyltin acetate, triphenyltin hydroxide, triphenyltin chloride, triphenyltin acetate, Phenyltin dimethyl dithiocarbamate, bistriphenyltin oxide, triphenyltin versatic acid, triphenyltin nicotinic acid, triphenyltin α, α-dibromosauccinate, triphenyltin monochloroacetate, tributyltin fluoride, bis(tributyltin) ) α
, σ-dibromsuccinate, tributyltin methacrylate copolymer, etc.]; Organochlorine compounds [DDT, BH
C, etc.]; thiuram compounds [tetraalkylthiuram disulfite, etc. 1; carbamate compounds (zinc dimethyl dithiocarbamate, etc.), cuprous oxide, etc., and one or more selected from the group consisting of: The blending amount of such a general antifouling agent is preferably 200 parts by weight or less per 100 parts by weight of the coating resin.

The antifouling paint composition of object (I) may optionally contain conventionally known coloring pigments (for example, red iron, titanium white, carbon, cyanine blue, cyanine green, etc.) and/or extender pigments (for example, talc, barida, etc.). , zinc white, etc.) may also be blended. Further, an organic solvent may be used to adjust the viscosity of the paint, but the type of solvent used is not particularly limited as long as it can dissolve or disperse the paint resin or plasticizer, and for example, Hydrocarbon solvents such as xylene and toluene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and ester solvents such as butyl acetate and ethyl acetate are used.

Since the object (I) of the present invention has an excellent control action against microorganisms, algae, aquatic organisms, etc. over a long period of time,
Shows excellent antifouling effect on underwater structures.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. Also,
% indicates weight %.

3 Example 1 Ethyl acetate looog and 516 g (2 mol) of 3,3,4°4-tetrachlorotetrahydrothiophene-1°-dioxide were dissolved with stirring, and 500 g of water was added. 1514 g (2 mol) of a 22.5% aqueous solution of sodium N,N-diethyldithiocarbamate was added dropwise over about 60 minutes, and this amount was cooled in a water cooling bath and maintained at 5 to 22°C. The mixture was further stirred for about 24 hours to obtain a slurry-like reaction solution. Add 500ml of water to the slurry precipitate obtained by filtration.
and methanol, washed and filtered, and heated to room temperature under reduced pressure (1
3.3.
-Dichloro-2,3-dihydro-1,1dioxythiophen-4-yl 306 g of N,N-diethyldithiocarbamate was obtained. In addition, the filtrate was left to stand and separated into two layers to obtain 200 g of the oil layer, the solvent was distilled off, ethyl acetate was added to make the total amount 635 g, and the mixture was redissolved and filtered to obtain a completely transparent brown solution. Ta. Recrystallize by standing at -10°C for 24 hours, filter the precipitate, wash with 200ml of 4 methanol, and dry at room temperature (10-20°C) under reduced pressure to further collect the white crystals of the target product. 125g was obtained. The obtained target product was analyzed by gas chromatography and found to have a purity of 99.9% or more.

Nuclear magnetic resonance spectrum (CDCQ,) δ; 4.0 nal,
Between 1.30-1.56ppm (C1-13-), between 3°74-3-67ppm (CH2) and 4.0000
-4-06pp CH2) signal.

Elemental analysis value; Actual value 32.5% 4.0 4.0 21.2 28.9 5-116°C Calculated value 32.3% 3.9 4.2 21.2 28.8 Elemental analysis value; U2 Example 2 1400 g of ethyl acetate and 722.5 g (2.8 mol) of 3,3,4°4-tetrachlorotetrahydrothiophene-1°l-dioxide were dissolved with stirring. N,
22.1 of sodium N-dibutyldithiocarbamate
% aqueous solution (2-8 mol) was added dropwise over about 60 minutes and this amount was maintained at 5-22°C in a water cooling bath. 2 more
Stirred for 4 hours.

The reaction solution was allowed to stand, separated into two layers, and the solvent was distilled off from the oil layer at 50° C. under reduced pressure to obtain about 1077 g of a crude product.

Add 3000 g of methanol to this crude product and dissolve it, -10'c! Let it stand for about 3 days and recrystallize it, about 37
0 g of 3,3-dichloro-2,3-dihydro-1,1-
White powder crystals of dioxythiophen 4-yl N,N-dibutyldithiocarbamate were obtained.

Actual value C40°H5°N 3°CJ 18°S 24°Melting point: 55-56°C 2 Calculated value 40.0% 5.4 3.6 18.2 24.6 Example 3 N of Example 1, 1514 g of a 22.5% aqueous solution of sodium N-diethyldithiocarbamate was added to N.

The procedure was repeated in the same manner as in Example 1 except that 1590 g (2 mol) of a 20% aqueous solution of potassium N-dimethyldithiocarbamate was substituted, and 3.3% of white powder crystals with a purity of 99.9% or higher were obtained.
-dichloro-2,3-dihydro-1,1-dioxythiophen-4-yl N.

27- 302g of N-dimethyldithiocarbamate was obtained.

Elemental analysis value; Actual value 27.9% 2.8 4.4 24.6 29.4 7-138°C Calculated value 27.4% 2.9 4.6 23.2 31.4 8 Maintained below . The reaction solution was filtered to remove salt, and the solvent was distilled off from the filtrate to obtain about 350 g of a brown solid crude product. This was subjected to column chromatography, eluted with tetrahydrofuran, and dried to give pale yellow powder crystals of 3,3-dichloro-2,3-hydro-1,1-dioxythiophene-4.
-yl ethyl xanthate was obtained.

Elemental analysis value; Actual value Calculated value CQ 32.2% 31.1%3
28.3 28.02 Example 4 500 mfl of acetone and 258 mfl of 3,3,4,4-tetrahydride-7ene-1,1-dioxide
g (1 mol) was stirred and dissolved. 150g (1 mol) of thorium ethylxanthate and 1500mQ of acetone
was added dropwise over about 60 minutes, and this amount was kept at 23°C or below while cooling in a water cooling bath. Stir for about 2 hours after addition and keep at 23°C2
Moreover, a new highly safe antifouling agent can be provided.

Claims (6)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^1, X^2 and X^3 are the same or different and represent halogen atoms or hydrogen atoms, Y is ▲ Mathematical formulas, chemical formulas, tables, etc. There is a group represented by ▼ or -OR^1 (in the formula, R^1 and R^2 are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent),
Z represents a hydrogen atom or a bond together with X^3]. (2) The compound according to claim (1), wherein Y is a di-C_1_-_4 alkylamino group. (3) The compound according to claim (1), wherein the halogen atom is a chlorine atom. (4) A compound represented by the formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents a halogen atom and R represents a C_1_-_4 alkyl group]. (5) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^1, X^2 and X^3 are the same or different and represent a halogen atom or a hydrogen atom, and X^4 represents a halogen atom] Compounds and formulas represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or -OR^1 (In the formula, R^1 and R^2 are the same or ▲Mathematical formula, chemical formula, There are tables, etc. ▼ Method for producing a compound represented by [wherein X^1, X^2, X^3 and Y have the same meanings as above, and Z represents a hydrogen atom or a bond together with X^3] . (6) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^1 and X^2 are the same or different halogen atoms or hydrogen atoms, and Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or -OR^1 (in the formula, R^1 and R^2
is the same or different and represents a group represented by a hydrogen atom or a hydrocarbon group which may have a substituent)], which is characterized by reacting a compound represented by the formula ▲ with a hydrogen halide. There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^1, X^2 and Y have the same meanings as above,
4 represents a halogen atom.