JP2003286272A - 1,2,4-benzothiadiazine-1,1-dioxide and method of producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing 1,2,4-benzothiadiazine-1,1-dioxide from readily available raw materials through shortened steps in high yield and to provide the new compound. <P>SOLUTION: In the method of producing of 1,2,4-benzothiadiazine-1,1-dioxide represented by general formula I, a compound represented by general formula II is allowed to react with an imidate represent by general formula III (wherein R1 is an alkyl or an aryl; R2 is a substituent; n is an integer of 0-4; R3 is a substituent; R4 is an alkyl which may be substituted or unsubsituted). Further, a compound represented by general formula (I-1) is provided (wherein R11 is an alkyl of 12 or more carbon atoms or an aryl of 6 or more carbon atoms; R13 is an alkoxycarbonyl, an aryloxy-carbonyl or carbamoyl). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is useful as a yellow coupler-intermediate for silver halide photographic light-sensitive materials, a synthetic intermediate for dyes, pharmaceuticals, agricultural chemicals, electronic materials, etc.
The present invention relates to a 2,4-benzothiadiazine-1,1-dioxide compound and a method for producing the same.

[0002]

2. Description of the Prior Art 1,2,4-Benzothiadiazine-1,1 in which the 2-position is a substituted or unsubstituted alkyl group or aryl group and the 3-position is a substituted or unsubstituted alkyl group.
-Dioxide compounds are yellow couplers and intermediates thereof for silver halide photographic light-sensitive materials, or dyes, pharmaceuticals, agricultural chemicals, as described in U.S. Pat. No. 3,841,880.
It is useful as a synthetic intermediate for electronic materials. As a method for synthesizing these compounds, US Pat. No. 3,841,8 has hitherto been known.
As described in No. 80, there was a method of reacting a 2-aminobenzenesulfonamide compound with a β, β-dialkoxyacrylic acid ester. However, in this method, the raw material β, β-dialkoxyacrylic acid ester is expensive and there is a problem in its availability. Also, J. Chi
n. Chem. Soc. , 45,805 (1998), a method of alkylating a 1,2,4-benzothiadiazine-1,1-dioxide compound having a hydrogen atom at the 2-position (or 4-position) is also known. However, this method has a drawback that it is a mixture of 2-position alkyl and 4-position alkyl. Furthermore, J. Med. Chem. , 6,
122 (1963), J. Org. Chem. , 51,
1967 (1986), Tetrahedron, 3
9, 2073 (1983), there was a method of reacting a 2-aminobenzenesulfonamide compound with an orthoester compound. However, in this reaction, when the starting orthoester has a substituent (for example, an alkoxycarbonyl group), there is a problem that the synthesis is difficult and the yield is low.

[0003]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a raw material that is easily available, in a short process and in a high yield.
It is intended to provide a method for producing a 2,4-benzothiadiazine-1,1-dioxide compound. Another object of the present invention is to provide a novel 1,2,4-benzobenzothiadiazine-1,1-dioxide compound produced by the method.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors, the following general formula (II) was obtained by reacting a compound represented by the following general formula (II) with a compound represented by the following general formula (III). It has been found that the above problems can be solved by a method for producing a compound represented by (I) and a compound represented by the following general formula (I-1). That is, the present invention is
(1) A compound represented by the following general formula (II) and an imidate compound represented by the following general formula (III) are reacted, 1,2 represented by the following general formula (I), Four
A method for producing a benzothiadiazine-1,1-dioxide compound,

[0005]

[Chemical 5]

In the formula, R1 represents a substituted or unsubstituted alkyl group or aryl group. R2 represents a substituent. n
Represents an integer of 0 or more and 4 or less. When n is 2 or more, a plurality of R2s may be the same or different and may bond to each other to form a ring. R3 represents a substituent.

[0007]

[Chemical 6]

In the formula, R1 represents a substituted or unsubstituted alkyl group or aryl group. R2 represents a substituent. n
Represents an integer of 0 or more and 4 or less. When n is 2 or more, a plurality of R2s may be the same or different and may bond to each other to form a ring.

[0009]

[Chemical 7]

In the formula, R3 represents a substituent. R4 represents a substituted or unsubstituted alkyl group. (2) The compound represented by the general formula (I) or the general formula (II), wherein R1 is a substituted or unsubstituted alkyl group having a total carbon number of 12 or more. (3) the general formula (I) and the general formula (III)
In the compound represented by the formula (3), R3 is an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group,
(4) 1,2,4-benzothiadiazine-1,1-dioxide compound represented by the following general formula (I-1), and

[0011]

[Chemical 8]

In the formula, R11 represents a substituted or unsubstituted alkyl group having 12 or more total carbon atoms or a substituted or unsubstituted aryl group having 6 or more total carbon atoms. R2 represents a substituent. n represents an integer of 0 or more and 4 or less. When n is 2 or more, a plurality of R2s may be the same or different and may bond to each other to form a ring. R13 represents an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group. (5) The 1,2,4-benzothi according to (4), wherein R11 is an unsubstituted alkyl group having a total carbon number of 18 or more, or a substituted alkyl group having a total carbon number of 12 or more. The present invention provides an asiazin-1,1-dioxide compound.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The compound represented by formula (I) of the present invention will be described in detail.

[0014]

[Chemical 9]

In the formula, R2 represents a substituent. n is 0 or more 4
Represents the following integers. When n is 2 or more, a plurality of R2s may be the same or different and may bond to each other to form a ring. Examples of the substituent of R2 include, for example,
Halogen atom, alkyl group (including cycloalkyl group, bicycloalkyl group), alkenyl group (including cycloalkenyl group, bicycloalkenyl group), alkynyl group,
Aryl group, heterocyclic group, cyano group, hydroxyl group,
Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group and anilino group) ), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group , A sulfo group, an alkyl or aryl sulfinyl group, an alkyl or aryl sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl group. Heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and a silyl group.

The above R2 group may be further substituted with a substituent, and examples of the substituent include the groups described above as the R2 group.

Examples of the R2 group will be further described below. As these substituents, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) , For example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-
Octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, 3- (2,4-di-t-.
Amylphenoxy) propyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, a polycycloalkyl group, for example A bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane- 3-
And a group having a polycyclic structure such as a tricycloalkyl group. A monocyclic cycloalkyl group and a bicycloalkyl group are preferable, and a monocyclic cycloalkyl group is particularly preferable. ),

Alkenyl group [A linear or branched substituted or unsubstituted alkenyl group, preferably having 2 to 3 carbon atoms.
0 is an alkenyl group, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, 2-cyclopentene-
1-yl, 2-cyclohexen-1-yl), a polycycloalkenyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, bicyclo [ Two
2,1] hept-2-en-1-yl, bicyclo [2,2]
2,2] oct-2-en-4-yl)], a tricycloalkenyl group or a bicycloalkenyl group, and a monocyclic cycloalkenyl group is particularly preferable. ) Alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl,
p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 7 membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or A condensed ring heterocyclic group, more preferably a heterocycle having a ring-constituting atom selected from a carbon atom, a nitrogen atom and a sulfur atom, and having at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom. And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-
Pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group,

Alkoxy group (preferably having 1 to 3 carbon atoms)
A substituted or unsubstituted alkoxy group of 0, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n
-Octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2
-Methylphenoxy, 2,4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably silyloxy group having 3 to 20 carbon atoms) And, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, and the heterocyclic moiety is the aforementioned heterocyclic group). The illustrated heterocycle is preferred, eg 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy group. , Acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethyl Carbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, N-n-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, For example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably having 7 to 3 carbon atoms).
A substituted or unsubstituted aryloxycarbonyloxy group of 0, for example, phenoxycarbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

Amino group (preferably, amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, heterocyclic ring having 0 to 30 carbon atoms) An amino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-
1,3,5-triazin-2-ylamino), an acylamino group (preferably a formylamino group, a carbon number of 1 to 3)
0 is a substituted or unsubstituted alkylcarbonylamino group, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino,
Benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N , N-dimethylaminocarbonylamino,
N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonyl). Amino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),

An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxy). Carbonylamino), sulfamoylamino group (preferably having 0 carbon atoms
To 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl or arylsulfonylamino groups (preferably A substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2, 3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a mercapto group,

Alkylthio group (preferably having a carbon number of 1 to
A substituted or unsubstituted alkylthio group of 30 such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms such as phenylthio,
p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic moiety is the heterocyclic group described above. The ring portion is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfur). Famoyl, N- (3-
Dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl,
N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group,

An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, Phenylsulfinyl,
p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) Groups, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl groups (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms). With a carbonyl group For example, phenoxycarbonyl, o- chlorophenoxy carbonyl, m- nitrophenoxy carbonyl, p-t-butyl-phenoxycarbonyl),

Alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably A substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-
Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),
Aryl or heterocyclic azo group (preferably having 6 to 6 carbon atoms)
30 substituted or unsubstituted arylazo groups, 3 carbon atoms
To 30 substituted or unsubstituted heterocyclic azo groups (the heterocyclic part is preferably the heterocyclic part described in the above heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,3. 4-thiadiazole-2
-Ylazo), an imide group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted imide group, for example, N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, Methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

Phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinyl Amino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably having 3 to 3 carbon atoms). Thirty substituted or unsubstituted silyl groups, including, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

Among the above groups, those having a hydrogen atom may be substituted with the above group after removing the hydrogen atom. Examples of such a group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, an arylsulfonylaminocarbonyl group, and specifically, methylsulfonylaminocarbonyl, p-methylphenyl. Examples thereof include sulfonylaminocarbonyl, acetylaminosulfonyl and benzoylaminosulfonyl groups.

R2 is preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonamide group, an acyl group, an acyloxy group. , A sulfonyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, a carboxyl group, and a sulfo group.

N represents an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and most preferably 0. .

In the general formula (I), R1 represents a substituted or unsubstituted alkyl group or aryl group. Here, in the substituted alkyl group or the substituted aryl group, examples of the substituent group substituting the alkyl group or the aryl group are the above R
The examples of the substituent of 2 are mentioned. The substituent of the substituted alkyl group in R1 is preferably an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, an alkylthio group, an arylthio group, a halogen atom, a sulfo group, a carboxyl group, an acyloxy group, an acyl group, an alkoxycarbonyl group. , A carbamoyl group, a heterocyclic group, more preferably an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, an alkylthio group, an arylthio group, a halogen atom, more preferably an aryl group, an alkoxy group, an aryloxy group, It is a hydroxy group, most preferably an alkoxy group or an aryloxy group. The substituent of the substituted aryl group in R1 is preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxyl group, an amino group, an acyl group, a sulfonyl group. , An alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamide group, a cyano group, a nitro group, a sulfo group, and a carboxyl group, and more preferably an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group. , An alkylthio group, an arylthio group, and a hydroxyl group.

The total carbon number of R1 (in the case of a substituted alkyl group, the carbon number of this substituent is also added) is preferably 12 or more and 60 or less, more preferably 16 or more and 50 or less in the case of a substituted or unsubstituted alkyl group, and 18 It is more preferably 40 or more and 40 or less. In the case of an aryl group (preferably a phenyl group which may have a substituent), the total carbon number (including the carbon number of this substituent in the case of a substituted aryl group) is preferably 6 or more and 60 or less, and 16 or more and 50 or more. The following is more preferable, and 18
It is more preferably 40 or more and 40 or less. R1 is preferably a substituted or unsubstituted alkyl group, more preferably an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group or an aryloxy group, and particularly preferably the above-mentioned preferred total carbon number.

In the general formula (I), R3 represents a substituent. Examples of the substituent include those mentioned above as examples of the substituent of R2. R3 is preferably an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), an aryloxycarbonyl group. (Preferably having 7 to 3 carbon atoms
A substituted or unsubstituted aryloxycarbonyl group of 0, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p
-T-butylphenoxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n). -Octylcarbamoyl, N- (methylsulfonyl) carbamoyl). More preferably, R3 is an alkoxycarbonyl group.

Examples of the substituents of the substituted alkoxycarbonyl group, the substituted aryloxycarbonyl group and the substituted carbamoyl group in R3 include the substituents represented by R2, preferably an alkyl group, an aryl group, a heterocyclic group and a halogen atom. Atom, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, nitro group, cyano group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, acyl group, acyloxy group, alkoxycarbonyl group, A sulfonyl group, a carboxyl group, and a sulfo group.

Of the compounds represented by the general formula (I),
The compound represented by the following general formula (I-1) is preferable.

[0036]

[Chemical 10]

In the formula, R11 is a substituted or unsubstituted alkyl group having a total carbon number of 12 or more (preferably a total carbon number of 12 or more and 60 or less), or a total carbon number of 6 or more (preferably a total carbon number of 6 or more and 60 or less). Represents a substituted or unsubstituted aryl group of, and these are the same as those described for the corresponding group in the general formula (I), and the preferable range and group are also the same as those in the general formula (I). R2 represents a substituent, and n
Represents an integer of 0 or more and 4 or less, and these are the same as those in the general formula (I), and the preferable range is also the same as in the general formula (I). When n is 2 or more, a plurality of R2 may be the same or different. R1
3 represents an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group, and each of these groups is the same as that described for the corresponding group in the general formula (I), and the preferable range and the group are also those of the general formula (I). Same as the case. Among the compounds represented by the general formula (I-1), among them, preferred compounds are unsubstituted R 11 having a total carbon number of 18 or more (preferably total carbon number of 18 to 40, more preferably total carbon number of 18 to 30). Alkyl group or total carbon number 1
2 or more [preferably a substituted alkyl group having a total carbon number of 12 to 60 (the substituent of the substituted alkyl group is, as described above, a preferred range of the substituent of the substituted alkyl group described in R1 of the general formula (I)]. Preferred)) is preferred,
Among the substituted alkyl groups, an alkoxy-substituted alkyl group or an aryloxy-substituted alkyl group is particularly preferable.

The compound represented by the general formula (I), preferably (I-1), is a synthetic intermediate of a dye (pigment), a drug,
It is useful as a synthetic intermediate for agricultural chemicals or electronic materials. Of these, dyes (pigments) obtained from the intermediates have a high extinction coefficient and are excellent in hue and fastness, so dyes (pigments) for images or couplers for obtaining the dyes or synthetic intermediates of the couplers. Useful as, among other things,
It is useful as a coupler (particularly a yellow coupler) for silver halide photographic light-sensitive materials or an intermediate thereof,
It is useful as a synthetic intermediate for a yellow coupler. The compound represented by formula (I) can also serve as a coupler of a silver halide photographic light-sensitive material depending on the group of R3. Examples of R3 include an alkoxycarbonyl group, an aryloxycarbonyl group and a carbamoyl group. Here, the compound represented by the general formula (I) may be directly used as a coupler, but the compound represented by the general formula (I)
In represent a _{-CH 2 -R3 -CH (X) -R3} ( wherein, X represents a group capable of being released by a coupling reaction with an oxidized product of a developing agent) is preferably used to convert into. When R3 is an alkoxycarbonyl group or an aryloxycarbonyl group as described above, this functional group is reacted with an aniline derivative to convert R3 into an N- (phenyl group which may have a substituent) carbamoyl group. conversion, further by converting the _-CH 2 -R3 in -CH (X) -R3, can be guided to the coupler is (or phenyl substituted) carbamoyl group R3 various N-. These conversion steps can be easily manufactured by a general manufacturing method in manufacturing a yellow coupler. For example, JP-A-7-242061 and JP-A-9-1
The method described in No. 89987 or a method similar thereto can be mentioned. The couplers produced in this manner are disclosed, for example, in JP-A-11-7109 and JP-A-11-30539.
No. 6, in the silver halide photographic light-sensitive material described in JP-A No. 11-84601, it is preferably applied as a yellow coupler.

Here, in particular, a compound represented by the general formula (I-1) (a compound acting as a coupler as described above) or a compound represented by the general formula (I-1) is used as a synthetic intermediate. The fastness of the dye obtained by incorporating the coupler produced through the steps into a silver halide color photographic light-sensitive material and performing color development treatment is R1
It is excellent when 1 is a substituted or unsubstituted alkyl group having 12 or more total carbon atoms or a substituted or unsubstituted aryl group having 6 or more total carbon atoms. The compound represented by the general formula (I-1) can be produced by the production method of the present invention for the compound represented by the general formula (I), and the compound obtained by the production method is preferable.

Next, the compound represented by formula (II) of the present invention will be explained in detail.

[0041]

[Chemical 11]

In the general formula (II), R1, R2 and n are the same as those described in the general formula (I), and the preferable ranges are also the same.

Next, the compound represented by formula (III) of the present invention will be explained in detail.

[0044]

[Chemical 12]

In the general formula (III), R3 has the same meaning as described in the general formula (I), and the preferred range is also the same. In the general formula (III), R4 is a substituted or unsubstituted alkyl group (R in the general formula (I)
It may be substituted with the substituent shown by 2, and is preferably an alkyl group having a total carbon number of 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10, for example, methyl, ethyl, n-propyl, Isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, 3-dodecyloxypropyl, 3- (2,4-di-t-amylphenoxy) propyl)). Represents R4 is preferably an unsubstituted alkyl group, more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and most preferably an ethyl group.

In the present invention, the preferred specific examples among the compounds represented by formula (I) are shown below, but the present invention is not limited thereto. In addition, the hydrogen atom of the active methylene part (CH ₂ part in which R3 of —CH ₂ —R3 is substituted) is C = in the heterocycle bonded to the active methylene part.
N atom nitrogen atom (1,2,4-benzothiadiazine-
The present invention also includes tautomers that are transferred onto the nitrogen atom at the 4-position of the 1,1-dioxide ring). In the chemical structural formula, Ph represents a phenyl group, Me represents a methyl group, and Et represents an ethyl group.

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

[0052]

[Chemical 18]

In the following description, when referring to the exemplified compounds shown above, the number (x) in parentheses attached to each exemplified compound is used to indicate "exemplified compound (x)". I decided to.

The manufacturing method of the present invention will be described in detail below. Specifically, the compound represented by the general formula (I) of the present invention is produced by the compound represented by the general formula (II) and the compound represented by the general formula (III) as shown below. However, by reacting them, an intermediate represented by the following general formula (A) is first formed, and then the intermediate represented by the general formula (A) is cyclized in the molecule. By reacting and removing the alcohol, a compound represented by the general formula (I) is produced. In the present invention, the intermediate represented by the general formula (A), which can be once formed, is not isolated but is continuously reacted in one pot (the same reaction vessel) to obtain the general formula (I).
The compound represented by the formula (1) may be produced, or the intermediate represented by the general formula (A) may be isolated, extracted, or concentrated to remove the reaction mixture, and then the intermediate or the reaction The mixture may be reacted under another condition to produce the compound represented by the general formula (I).

[0055]

[Chemical 19]

Here, in the general formula (A), R1, R
2 and R3 are the same as in the general formula (I), and R4 and n are the same as in the general formula (III).

The general formula (I
The compound represented by I) and the compound represented by the general formula (III) can be easily synthesized by various known methods.
The compound represented by the general formula (II) can be most commonly synthesized by reacting ortho-nitrobenzenesulfonyl chlorides with amines and then reducing the nitro group.
The compound represented by the general formula (III) is most generally prepared by isolating a cyanoacetic acid ester as a hydrogen chloride salt by blowing hydrogen chloride gas in a solvent such as ether in the presence of an alcohol to cause a reaction. Easily synthesized.

In the production method of the present invention, the general formula (II
The compound represented by I) may be used in a free state, but is preferably used in the form of a salt with various acids, and more preferably used as a hydrogen chloride salt. Also, together with the compound represented by the general formula (III) in a free state,
It is also preferable to add an acid and react. Examples of the acid used here include sulfuric acid, acetic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid and the like. Also, in the step of producing the compound represented by the general formula (I) from the intermediate represented by the general formula (A), it is preferable to react in the presence of an acid, and the acid used here is sulfuric acid. , Acetic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, ammonium chloride and the like. These acids may be used alone or in combination of two or more. The amount of the acid used is preferably 0.01 to 1 per 1 mol of the compound represented by the general formula (III) or 1 mol of the intermediate represented by the general formula (A).
00 mol, more preferably 0.1 to 20 mol, further preferably 0.2 to 10 mol, particularly preferably 0.5 to 5
Used in molar proportions.

In general, the compound represented by the general formula (II) and the compound represented by the general formula (III) are 100 compounds represented by the general formula (II): : 1 to 1: 100, preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and most preferably 1 : Used in a molar ratio of 1 to 1: 3.

The reaction in the production method of the present invention may be carried out in the absence of a solvent, but may preferably be carried out by dissolving or dispersing in a suitable solvent. Examples of the solvent that can be used in the reaction of the present invention include water, alcohol solvents (for example, methanol and isopropanol), chlorine solvents (for example, dichloromethane and chloroform), aromatic solvents (for example, benzene, toluene and chlorobenzene). , Amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide), ureido solvents (for example, 1,3-dimethyl-2-imidazolidinone), nitrile solvents (for example, acetonitrile), ethers System solvents (for example, diethyl ether, tetrahydrofuran), sulfone solvents (for example, sulfolane),
Examples thereof include sulfoxide solvents (eg, dimethyl sulfoxide), phosphoric acid amide solvents (eg, hexamethylphosphoric triamide), and hydrocarbon solvents (eg, hexane, cyclohexane).

These solvents may be used alone or in combination of two or more. The amount of solvent used is
Per part by mass of the compound represented by the general formula (II) or per part by mass of the intermediate represented by the general formula (A), preferably 0.1 to 1000 parts by mass, more preferably 0.5 to 100 parts by mass. It is used in an amount of 100 parts by mass, more preferably 1 to 50 parts by mass.

In the reaction of the compound represented by the general formula (II) with the compound represented by the general formula (III), it is preferable to use an alcohol solvent, and ethanol is most preferable. In the step of synthesizing the compound represented by the general formula (I) from the intermediate represented by the general formula (A), an aromatic solvent is preferable, toluene and xylene are more preferable, and xylene is most preferable.

The reaction temperature of this reaction is not particularly limited, but it can be carried out in the range of -50 ° C to 300 ° C, preferably -10 ° C to 250 ° C, and more preferably 0 ° C. It can be carried out in the range of 200 ° C.

The reaction time of this reaction is not particularly limited, but it can be carried out in the range of 1 minute to 100 hours, preferably 10 minutes to 50 hours, and more preferably 30 minutes to 10 hours. Can be implemented.

[0065]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Production of Exemplified Compound (1) Exemplified compound (1) was produced as follows.

[0067]

[Chemical 20]

A solution of 18.9 g of compound (A-1), 39.1 g of hydrochloride of imino ether (A-0), and 200 ml of ethyl alcohol was stirred under heating with reflux for 1 day. Furthermore, 19.2 g of hydrochloride of imino ether was added and further heated under reflux.
It was stirred for 1 day. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallized from a mixed solvent of ethyl acetate and hexane to obtain 21.0 g of Exemplified compound (1). Yield 73.3%. m. p. 127-
128 ° C.

Example 2 Production of Exemplified Compound (9) Exemplified compound (9) was produced as follows.

[0070]

[Chemical 21]

111 g of compound (B-1), 68.4 g of hydrochloride of imino ether (A-0), ethyl alcohol 1
50 ml of the solution was stirred with heating under reflux for 1 hour. Furthermore, 4.9 g of hydrochloride of imino ether was added, and the mixture was further heated under reflux for 3
Stir for 0 minutes. After cooling, suction filtration was carried out, 100 ml of p-xylene was added to the filtrate, and the mixture was heated under reflux for 4 hours while distilling off ethanol. The reaction solution was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as an eluent, and crystallized from methanol to give 93.1 g.
The exemplified compound (9) was obtained. Yield 69.0%. m. p.
76-77 ° C.

Example 3 Production of Exemplified Compound (7) Exemplified compound (7) was produced as follows.

[0073]

[Chemical formula 22]

Compound (C-1) 200 g, imino ether (A-0) hydrochloride 46 g, ethyl alcohol 60
0 ml of the solution was stirred under heating under reflux for 30 minutes. Further, 138 g of hydrochloride of imino ether was added every 30 minutes in three times, and the mixture was stirred for 30 minutes while heating under reflux. p-xylene 650
ml was added, ethanol was distilled off, and the mixture was heated under reflux for 5 hours. The reaction solution was extracted with ethyl acetate and washed with water and saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and crystallized from methanol to obtain 176 g of Exemplified compound (7). Yield 71.9%. m. p. 80 ~
81 ° C.

[0075]

Industrial Applicability According to the present invention, it is possible to provide a method for producing a 1,2,4-benzothiadiazine-1,1-dioxide compound from an easily available raw material in a short step and in a high yield. Furthermore, according to the production method of the present invention, a yellow coupler intermediate for a silver halide photographic light-sensitive material, a dye, a medicine,
Novel 1,2,4 as synthetic intermediates for agricultural chemicals, electronic materials, etc.
A benzothiadiazine-1,1-dioxide compound can be provided.

Claims (2)

[Claims] 1. A compound represented by the following general formula (II), characterized by reacting a compound represented by the following general formula (II) with an imidate compound represented by the following general formula (III): Process for producing 2,4-benzothiadiazine-1,1-dioxide compound. [Chemical 1] In the formula, R1 represents a substituted or unsubstituted alkyl group or aryl group. R2 represents a substituent. n represents an integer of 0 or more and 4 or less. When n is 2 or more, a plurality of R2s may be the same or different and may bond to each other to form a ring. R3 represents a substituent. [Chemical 2] In the formula, R1 represents a substituted or unsubstituted alkyl group or aryl group. R2 represents a substituent. n represents an integer of 0 or more and 4 or less. When n is 2 or more, a plurality of R2s may be the same or different and may bond to each other to form a ring. [Chemical 3] In the formula, R3 represents a substituent. R4 represents a substituted or unsubstituted alkyl group. 2. A compound represented by the following general formula (I-1):
2,4-benzothiadiazine-1,1-dioxide compound. [Chemical 4] In the formula, R11 represents a substituted or unsubstituted alkyl group having 12 or more carbon atoms in total or a substituted or unsubstituted aryl group having 6 or more carbon atoms in total. R2 represents a substituent. n represents an integer of 0 or more and 4 or less. When n is 2 or more, a plurality of R2s may be the same or different and may bond to each other to form a ring. R13 represents an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group.