JP2012051817A - Production method of acid halide and acid halide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for inexpensively producing an acid halide having a leaving group and a bulky group with high accuracy in selectiveness.SOLUTION: The production method of the acid halide includes a process for obtaining a compound expressed by a general formula (II) by making a compound expressed by a general formula (III) and the acid halide react with each other, and expressed by a general formula (I) by making a compound expressed by the general formula (II) and an acid halide agent react with each other. In the general formula (I), A denotes a bivalent coupling group which is obtained by extracting one atom from a univalent substituent whose Es' value being a three-dimensional parameter is not smaller than 1.5, and Xdenotes a halogen atom. Ldenotes the leaving group. In the general formula (II), A and Lare synonymous with A and Lin the general formula (I), respectively. In the general formula (III), A and Lare synonymous with A and Lin the general formula (I), respectively.

Description

  The present invention relates to a method for producing an acid halide, and an acid halide.

Acid halides are actively used as synthetic intermediates for functional compounds such as medicines, agricultural chemicals and pigments. In particular, the acid halide having a bulky group can make a specific portion of the functional compound bulky. As a result, for example, it can be expected to impart functionality such as sharpening of hue by suppressing molecular rotation, improvement of chemical resistance and weather resistance by protecting vulnerable parts of functional compounds, etc., so acid halides having bulky groups Is useful. Furthermore, an acid halide having a leaving group and a bulky group can introduce a functional group such as an alkali-soluble group or a polymerizable group by substituting the leaving group. Because it becomes possible, it is very useful.
As a method for producing an acid halide having a bulky group, there is a method in which an ester compound having a bulky group is hydrolyzed under alkaline conditions and the resulting carboxylic acid is reacted with thionyl chloride (for example, non-patent literature). 1). However, when producing an acid halide having a leaving group using this method, there is a problem that the leaving group is eliminated during the production of the carboxylic acid, resulting in a decrease in the yield of the target product. In particular, an ester compound having a bulky group has a high hydrolysis rate, and the elimination reaction proceeds remarkably. Therefore, it is very difficult to synthesize an acid halide having a leaving group and a bulky group. It was difficult. In order for the leaving group to suppress elimination, it can be considered that the conditions for producing a carboxylic acid having a bulky group are mild. As a method for producing a carboxylic acid having a bulky group, a method in which an acid amide is reacted with sodium nitrite (see Non-Patent Document 2), a method in which a ketone is oxidized with nitric acid (see Non-Patent Document 3), a Grignard reagent and dioxide dioxide Although a method of reacting carbon (see Non-Patent Document 3) has been reported, these reactions also cause a leaving group to react, resulting in a decrease in the yield of the target product, a dangerous reaction, and a large amount There was a problem that it was not suitable for manufacturing on a scale.
As a synthesis example of a carboxylic acid having a leaving group, a method of hydrolyzing an ester using trimethylsilyl iodide (see Patent Document 1) has been reported, but trimethylsilyl iodide is expensive and bulky. In the case of producing a carboxylic acid having an acid, there is a problem that the production cost is high because the reaction requires a long time.
Patent Document 1 describes the synthesis of a carboxylic acid chloride having a chlorine atom as a leaving group, but none of the described carboxylic acid chlorides have a substituent or about the methyl group. There is no known method for synthesizing an acid halide having a small substituent, a leaving group, and a bulky group.

US Pat. No. 6,204,278

J. et al. Am. Chem. Soc. 1984, 106, 1010. J. et al. Am. Chem. Soc. 1957, 79, 2530. Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry, 1974, 1525.

This invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, the first object of the present invention is to provide a method capable of producing an acid halide having a leaving group and a bulky group at low cost and high selectivity. The second object of the present invention is to provide a halide having a leaving group and a bulky group produced by the production method of the present invention.
In the present invention, the “bulky group” refers to a divalent linking group obtained by removing one hydrogen atom from a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more.

  As a result of examining various synthetic methods in detail, the present inventors have obtained a step of obtaining a carboxylic acid having a specific structure by reacting a specific aldehyde compound with an oxidizing agent, and converting the carboxylic acid having a specific structure into an acid halogenating agent. It has been found that an acid halide having a leaving group and a bulky group, which has been difficult to produce, can be produced at low cost and with high selectivity by a step of obtaining an acid halide by reacting.

Specific means for solving the above problems are as follows.
<1> A step of obtaining a compound represented by the following general formula (II) by reacting a compound represented by the following general formula (III) with an oxidizing agent, and represented by the following general formula (II): And a step of obtaining a compound represented by the following general formula (I) by reacting the compound with an acid halogenating agent, and a method for producing an acid halide.

In the general formula (I), A represents a divalent linking group obtained by removing one atom from a monovalent substituent having a steric parameter -Es' value of 1.5 or more. X ¹ represents a halogen atom. L ¹ represents a leaving group.

In formula (II), A and ^{L 1} are the same meanings as A and ^{L 1} in the general formula (I).

In general formula (III), A and L ¹ are respectively synonymous with A and L ¹ in general formula (I).
<2> The compound represented by the general formula (I) is a compound represented by the following general formula (IV), and the compound represented by the general formula (II) is represented by the following general formula (V): The method for producing an acid halide according to <1>, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (VI):

In general formula (IV), R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. R ³ represents an alkylene group. X ¹ and ^{L 1} are the same respectively as ^{X 1} and ^{L 1} in the general formula (I).

In the general formula ^(V), R ^1, R 2, ^{R 3} and ^{L 1} are respectively ^{R 1,} R 2, ^{R 3} and ^{L 1} synonymous in the general formula (IV).

In the general formula ^(VI), R ^1, R 2, ^{R 3} and ^{L 1} are respectively ^{R 1,} R 2, ^{R 3} and ^{L 1} synonymous in the general formula (IV).
<3> Further, a step of obtaining a compound represented by the general formula (VI) by reacting a compound represented by the following general formula (VII) with a compound represented by the following general formula (VIII): The manufacturing method of the acid halide as described in <2> containing this.

In the general formula (VII), ^{R 1} and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in the general formula (IV).

In the general formula (VIII), ^{R 3} and ^{L 1} are the same meanings as ^{R 3} and ^{L 1} in the general formula (IV). L ² represents a leaving group.
<4> Reaction temperature for the step of obtaining the compound represented by the general formula (VI) by reacting the compound represented by the general formula (VII) with the compound represented by the general formula (VIII) Is a method for producing an acid halide according to <3>, wherein the temperature is from -20 ° C to 10 ° C.
<5> Any one of <1> to <4>, wherein the oxidizing agent is an oxidizing agent selected from the group consisting of potassium permanganate, hydrogen peroxide, sodium chlorite, or a mixture of two or more thereof. A method for producing an acid halide according to 1.
<6> The method for producing an acid halide according to any one of <1> to <5>, wherein the acid halogenating agent is an acid halogenating agent selected from the group consisting of thionyl chloride, phosphoryl chloride, or oxalyl chloride. .
<7> A compound represented by the following general formula (I) obtained by the production method according to any one of <1> to <6>.

In the general formula (I), A represents a divalent linking group obtained by removing one atom from a monovalent substituent having a steric parameter -Es' value of 1.5 or more. X ¹ represents a halogen atom. L ¹ represents a leaving group.
<8> A compound represented by the following general formula (IV) obtained by the production method according to any one of <2> to <6>.

In general formula (IV), R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. R ³ represents an alkylene group. X ¹ and ^{L 1} are the same respectively as ^{X 1} and ^{L 1} in the general formula (I).

  Since the acid halide having a leaving group and a bulky group can be obtained with high purity by the method for producing a specific acid halide according to the present invention, it can be used for color filters, printing dyes, inkjet dyes, medicines and agricultural chemicals. As a product, it is particularly effective as a synthetic intermediate for functional compounds that require high purity.

  According to the production method of the present invention, an acid halide having a very useful leaving group and a bulky group can be produced at low cost and with high selectivity. Moreover, the production method of the present invention can provide an acid halide having a high-purity leaving group and a bulky group.

  Hereinafter, the method for producing an acid halide having a leaving group and a bulky group and the acid halide of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value, respectively.
Moreover, in the description of groups (atomic groups) in this specification, the description that does not indicate substitution and non-substitution includes those that have a substituent as well as those that do not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Further, “the number of carbon atoms of a certain functional group” represents the total number of carbon atoms of the functional group excluding the carbon number of the substituent.

The method for producing an acid halide having a specific structure according to the present invention comprises a step of obtaining a compound represented by the general formula (II) by reacting a compound represented by the general formula (III) with an oxidizing agent, And a step of obtaining a compound represented by the general formula (I) by reacting the compound represented by II) with an acid halogenating agent.
Hereinafter, the compound represented by the general formula (I), the general formula (II) and the general formula (III) and the production method will be described in detail.

<Compound represented by formula (I)>

In the general formula (I), A represents a divalent linking group obtained by removing one atom from a monovalent substituent having a steric parameter -Es' value of 1.5 or more. X ¹ represents a halogen atom. L ¹ represents a leaving group.

The steric parameter (-Es' value) in the present invention is a parameter representing the steric bulk of the substituent, and is described in literature (JAMacphee, et al, Tetrahedron, Vol. 34, pp3553-3562, edited by Ikuo Fujita, Chemical Special Edition 107). Activity correlation and drug design, published on February 20, 1986 (Chemical Doujin)) -Es' value is used. The -Es' value of A in the general formula (I) of the present invention includes 1.5 or more, preferably 2.0 or more, more preferably 3.5 or more, particularly preferably. 5.0 or more.
Specific examples of the monovalent substituent having a steric parameter (-Es' value) of 1.5 or more are given below, but the present invention is not limited thereto.
A in the present invention represents, for example, a divalent linking group obtained by removing one hydrogen atom or halogen atom from the substituents exemplified below, but is not limited thereto.

X ¹ represents a halogen atom, and from the viewpoints of ease of handling and the cost of the acid halogenating agent used, a chlorine atom and a bromine atom are particularly preferable, and a chlorine atom is most preferable.
L ¹ represents a leaving group. Examples of the leaving group include known leaving groups, but halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), sulfonyloxy groups (for example, mesyl group, tosyl group, trifluoromethanesulfonyloxy group, etc.) Is preferable, a chlorine atom and a bromine atom are more preferable, and a chlorine atom is most preferable.

  The compound represented by the general formula (I) is preferably a compound represented by the following general formula (IV).

<Compound represented by formula (IV)>

In general formula (IV), R ¹ and R ² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. R ³ represents an alkylene group. X ¹ and ^{L 1} are the same respectively as ^{X 1} and ^{L 1} in the general formula (I).

The alkyl group in R ¹ and R ² may be linear, branched or cyclic, and examples thereof include linear or branched substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms and carbon numbers. Examples include 3 to 30 substituted or unsubstituted cycloalkyl groups.
When R ¹ and R ² represent a linear or branched alkyl group, it is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, An n-octyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group and the like can be mentioned, but a linear or branched substituted or unsubstituted alkyl group having 2 to 20 carbon atoms is preferable. A substituted ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like are preferable.

When R ¹ and R ² represent a cyclic alkyl group, it is a substituted or unsubstituted cycloalkyl group, and the cycloalkyl group is a cycloalkyl group having 3 to 30 carbon atoms excluding the carbon atoms of the substituent. preferable. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.

  Examples of the substituent of the alkyl group having a substituent include a halogen atom, alkyl group, alkenyl 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, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfa Moylamino group, alkylsulfonylamino group or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group or arylsulfinyl group, alkylsulfuric group Nyl group or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, arylazo group or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group And a silyl group.

The said substituent of the alkyl group which has a substituent is demonstrated still in detail below.
A halogen atom (for example, a fluorine atom, 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, a methyl group, Ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms Group (for example, cyclohexyl group, cyclopentyl group), polycycloalkyl group (for example, bicycloalkyl group (preferably, substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (for example, bicyclo [1,2,2] Heptan-2-yl group, bicyclo [2,2,2] octane-3-yl group)) or tricycloalkyl group), preferably Monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

An alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms (for example, vinyl group, allyl group, prenyl group, geranyl group, oleyl group), 30 substituted or unsubstituted cycloalkenyl groups (for example, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group), polycycloalkenyl groups (for example, bicycloalkenyl group (preferably having 5 to 5 carbon atoms) 30 substituted or unsubstituted bicycloalkenyl groups (for example, bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group) )) And tricycloalkenyl groups), among which monocyclic cycloalkenyl groups are particularly preferred).

An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, a trimethylsilylethynyl group),

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

Alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group) An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy group, 2-methylphenoxy group, 2,4-di-t-amylphenoxy group, 4-t -Butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy group, t-butyldimethylsilyloxy group ), A heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy having 2 to 30 carbon atoms) In a heterocyclic part is preferably as described in the heterocyclic portion described above heterocyclic group, e.g., 1-phenyl-5-oxy group, 2-tetrahydropyranyloxy group),

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy group, acetyl An oxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, a p-methoxyphenylcarbonyloxy group), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxycarbonyloxy group ( Preferably, A substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 primes, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryloxycarbonyloxy group (preferably, A substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 1 to 30 carbon atoms) Yes, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, N-1,3,5-triazin-2-ylamino group), acylamino group (preferably A formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino group, acetylamino group, and pivaloylamino. Group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenyl group A carbonylamino group), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonyl group). An amino group, a morpholinocarbonylamino group), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, or a t-butoxycarbonylamino group. N-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group),

Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonyl Amino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N, N-dimethylaminosulfonylamino group, N -N-octylaminosulfonylamino group), alkylsulfonylamino group or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms) Sulfonylamino group For example, methylsulfonylamino group, butylsulfonyl group, phenylsulfonylamino group, 2,3,5-trichlorophenyl sulfonylamino group, p- methylphenyl sulfonylamino group), a mercapto group,

An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group or an n-hexadecylthio group), an arylthio group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms); An arylthio group, for example, a phenylthio group, a p-chlorophenylthio group, an m-methoxyphenylthio group), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, Is preferably a heterocyclic moiety described in the above heterocyclic group, for example, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituent having 0 to 30 carbon atoms or An unsubstituted sulfamoyl group such as N-ethylsulfamoyl group, N- (3-dodecyloxy) Propyl) sulfamoyl group, N, N- dimethylsulfamoyl group, N- acetyl sulfamoyl group, N- benzoylsulfamoyl group, N- (N'-phenylcarbamoyl) sulfamoyl group), a sulfo group,

An alkylsulfinyl group or an 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, such as a methylsulfinyl group or an ethylsulfinyl group; , Phenylsulfinyl group, p-methylphenylsulfinyl group), alkylsulfonyl group or arylsulfonyl group (preferably substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms) Group, for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, carbon Number 7-30 Substituted or unsubstituted arylcarbonyl group, for example, acetyl group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group), aryloxycarbonyl group (preferably, A substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group),

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl group (preferably Is a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, such as carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methyl (Sulfonyl) carbamoyl group), arylazo group or heterocyclic azo group (preferably substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic moiety is The heterocyclic moiety described above for the heterocyclic group is preferred), For example, a phenylazo group, a p-chlorophenylazo group, a 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, For example, N-succinimide group, N-phthalimide group), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group) A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group),

Phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group), phosphinylamino A group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group), a silyl group (preferably a carbon number of 3 -30 substituted or unsubstituted silyl groups, for example, trimethylsilyl group, t-butyldimethylsilyl group, phenyldimethylsilyl group).

  Among the above substituents, those having a hydrogen atom may be substituted with any of the above groups by removing this. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specifically, a methylsulfonylaminocarbonyl group, p- Examples include methylphenylsulfonylaminocarbonyl group, acetylaminosulfonyl group, and benzoylaminosulfonyl group.

The alkenyl group in R ¹ and R ² may be linear, branched or cyclic, and examples thereof include a substituted or unsubstituted alkenyl group.
When R ¹ and R ² represent a linear or branched alkenyl group, an alkenyl group having 2 to 30 carbon atoms excluding the carbon atoms of the substituent is preferable. Examples of alkenyl groups include allyl, prenyl, geranyl, oleyl and the like. Examples of the substituent that these alkenyl groups may have include those listed as examples of the substituent of the alkyl group.

When R < ¹ > and R < ² > represent a cyclic alkenyl group, the C5-C20 cycloalkenyl group except the carbon atom of a substituent is preferable. Examples of the cycloalkenyl group include a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a cyclodecenyl group, and the like. Examples of the substituent that the cycloalkenyl group may have include those exemplified as the substituent of the alkyl group.

The alkynyl group in R ¹ and R ² includes an alkynyl group having a substituent and an unsubstituted alkynyl group. An alkynyl group having 2 to 30 carbon atoms excluding the carbon atom of the substituent is preferable. Examples of the alkynyl group include ethynyl group, propargyl group and the like. Examples of the substituent that these alkynyl groups may have include those listed as examples of the substituent of the alkyl group.

The aryl group in R ¹ and R ² includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 30 carbon atoms excluding the carbon atoms of the substituent is preferable. Examples of the aryl group include a phenyl group, a p-tolyl group, and a naphthyl group. Examples of the substituent that these aryl groups may have include those listed as examples of the substituent of the alkyl group.

The heterocyclic group in R ¹ and R ² includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. As the heterocyclic group, a heterocyclic group having 6 to 30 carbon atoms excluding the carbon atoms of the substituent is preferable. Examples of the heterocyclic group include a pyridyl group, an imidazolyl group, a pyroyl group, a pyrazolyl group, a furanyl group, a tetrahydrofuranyl group, and the like. Examples of the substituent that these heterocyclic groups may have include those listed as examples of the substituent of the alkyl group.
R ¹ and R ² are particularly preferably alkyl groups, and more preferably an alkyl group having 2 to 10 carbon atoms.

R ³ in the general formula (IV) may be linear, branched or cyclic, and represents a substituted or unsubstituted alkylene group.
The linear or branched alkylene group for R ³ includes an alkylene group having a substituent and an unsubstituted linear or branched alkylene group. As an alkylene group, a C1-C30 linear or branched alkylene group is preferable, a C2-C20 linear or branched alkylene group is preferable, and a C2-C5 linear or branched alkylene group is preferable. Most preferred is an alkylene group. Examples of the substituent that these alkylene groups may have include those listed as examples of the substituent of the alkyl group.

As the cyclic alkylene group in R ^3, the number of carbon atoms, excluding the carbon atoms of the substituent is preferably a cycloalkylene group having 3 to 30. Examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and the like. Examples of the substituent that these cycloalkylene groups may have include those listed as examples of the substituent of the alkyl group.
R ³ is particularly preferably a linear or branched alkylene group.

^{X 1} and ^{L 1} in the general formula (IV) has the same meaning as ^{X 1} and ^{L 1} in Formula (I), and preferred ranges are also the same.

In the general formula (IV), R ¹ is an alkyl group having 2 to 10 carbon atoms, R ² is an alkyl group having 2 to 10 carbon atoms, and R ³ is an alkylene group having 2 to 10 carbon atoms. It is preferable that X ¹ is a chlorine atom or a bromine atom, and L ¹ is a chlorine atom or a bromine atom. R ¹ is an alkyl group having 2 to 5 carbon atoms, R ² is an alkyl group having 2 to 5 carbon atoms, R ³ is an alkylene group having 2 to 5 carbon atoms, and X ¹ is Most preferably, it is a chlorine atom and L ¹ is a chlorine atom.

Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited thereto.
In the table of exemplary compounds, “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, “Bu” represents a butyl group, and “Ph” represents a phenyl group.

<Compound represented by formula (II)>

In formula (II), A and ^{L 1} have the same meanings as A and ^{L 1} in Formula (I), and preferred ranges are also the same.

  The compound represented by the general formula (II) is preferably a compound represented by the general formula (V).

<Compound represented by formula (V)>

In the general formula ^(V), R ^1, R 2, ^{R 3} and ^{L 1} have the same meanings as ^{R 1,} R 2, ^{R 3} and ^{L 1} in formula (IV), and preferred ranges are also the same.

  Specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

<Compound represented by formula (III)>

In general formula (III), A and L ¹ are synonymous with A and L ¹ in general formula (I), respectively, and preferred ranges thereof are also the same.

  The compound represented by the general formula (III) is preferably represented by the general formula (VI).

<Compound represented by formula (VI)>

In the general formula ^(VI), R ^1, R 2, ^{R 3} and ^{L 1} have the same meanings as ^{R 1,} R 2, ^{R 3} and ^{L 1} in formula (IV), and preferred ranges are also the same.

  Specific examples of the compound represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

  Hereinafter, the production method of the present invention will be described in detail.

<The process of obtaining the compound represented by general formula (II) by making the compound represented by general formula (III) react with an oxidizing agent>
The production method of the present invention includes a step of obtaining a compound represented by the general formula (II) by reacting the compound represented by the general formula (III) with an oxidizing agent (hereinafter referred to as “oxidation step” as appropriate). . As the oxidizing agent used in the oxidation step, a known oxidizing agent can be used. For example, air, pure oxygen, potassium permanganate, chromium oxide, potassium dichromate, hydrogen peroxide, urea hydrogen peroxide adduct / Inorganic and organic peroxides such as phthalic anhydride, t-butyl hydroperoxide, cumene hydroperoxide, selenium dioxide, lead (IV) acetate, t-butyl hypochlorite, sodium hypochlorite, sodium chlorite These oxidizing agents may be used alone or in combination of two or more. In particular, sodium chlorite, a mixture of sodium chlorite and hydrogen peroxide is preferable, and sodium chlorite is most preferable.

  The amount of the oxidizing agent used depends on the oxidation strength of the oxidizing agent to be used and cannot be uniquely determined, but is preferably 1 to 100 mol with respect to 1 mol of the compound represented by the general formula (III). It is more preferably 1 to 10 mol, and most preferably 1 to 5 mol. The reaction temperature is preferably -5 to 50 ° C, more preferably 0 to 40 ° C. The reaction time is preferably 0.5 to 10 hours from the viewpoint of productivity. The end point of the reaction can be determined by NMR, gas chromatography, high performance liquid chromatography or the like.

  The oxidation process of the present invention may use additives that trap active by-products. The additive for trapping active by-products can be used without particular limitation. For example, when sodium chlorite is used as the oxidizing agent, 2-methyl-2-butene can be used as an additive for capturing hypochlorous acid and chlorine as by-products. The addition amount of the additive for trapping the active by-product is preferably 1 to 1000 mol, and most preferably 1 to 200 mol, per 1 mol of the oxidant.

  In the oxidation step of the present invention, a pH buffer can be used to accelerate the progress of the oxidation reaction. Although there is no restriction | limiting in particular as a pH buffering agent, For example, sodium dihydrogen phosphate, potassium dihydrogen phosphate, an acetic acid etc. are mentioned. The addition amount of the additive is preferably 1 to 100 mol, more preferably 1 to 10 mol, and more preferably 1 to 5 mol with respect to 1 mol of the compound represented by the general formula (III). Is most preferred.

  As the solvent used in the oxidation step of the present invention, any solvent can be used without particular limitation as long as the oxidizing agent to be used is not deactivated. Examples thereof include ethyl acetate, methanol, tert-butanol, water, and acetic acid. These solvents may be used alone or in combination of two or more. It is particularly preferable to use a mixed solvent of tert-butanol and water.

  In the oxidation step of the present invention, a phase transfer catalyst may be used. The phase transfer catalyst is not particularly limited and can be used. Examples of the phase transfer catalyst include quaternary ammonium compounds, crown ethers, phosphonium compounds, pyridinium compounds and the like, and quaternary ammonium compounds are preferred from the viewpoint of production cost.

  The compound represented by the general formula (II) may be purified by an operation such as distillation or recrystallization, but is preferably used as it is in the next step without isolation from the viewpoint of production cost.

<The process of obtaining the compound represented by general formula (I) by making the compound represented by general formula (II) react with an acid halogenating agent>
Acid halogenation used in the step of obtaining the compound represented by the general formula (I) by reacting the compound represented by the general formula (II) with an acid halogenating agent (hereinafter referred to as “acid halogenation step” as appropriate) The agent represents a known compound capable of converting a carboxylic acid into an acid halide, and includes compounds described in Fourth Edition Experimental Chemistry Course 22 Organic Synthesis IV Acids / Amino Acids / Peptides 115-127. Thionyl chloride Oxalyl chloride, oxalyl chloride and phosphoryl chloride are preferred, and thionyl chloride is most preferred. The amount of the acid halogenating agent used is preferably 1 to 5 mol, more preferably 1 to 2 mol, per 1 mol of the compound represented by the general formula (II). The reaction temperature is preferably 0 to 100 ° C, more preferably 10 to 70 ° C, and most preferably 20 to 50 ° C. The reaction time is preferably 0.5 to 10 hours.

  In order to activate the acid halogenating agent, an additive may be further added. As the additive, N, N-dimethylformamide and pyridine are preferable. The addition amount of the additive is preferably 0.001 to 1 mol, and most preferably 0.01 to 0.5 mol, per 1 mol of the compound represented by the general formula (II).

  The acid halogenation step of the present invention is preferably performed without a solvent from the viewpoint of productivity, but may be performed in the presence of a solvent. The solvent to be used is not particularly limited, but an aliphatic hydrocarbon solvent (for example, hexane, heptane, etc.), an aromatic solvent (for example, benzene, toluene, xylene, mesitylene, chlorobenzene, etc.), an ester solvent (for example, , Ethyl acetate, butyl acetate, etc.), ether solvents (eg, tetrahydrofuran, diethyl ether, dibutyl ether, diphenyl ether, etc.), amide solvents (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl) 2-pyrrolidone, N-ethyl-2-pyrrolidone, etc.) and sulfur-containing solvents (for example, dimethyl sulfoxide, sulfolane, etc.) and the like, and aromatic solvents and ester solvents are particularly preferable.

  The compound represented by the general formula (I) is preferably purified by distillation, recrystallization or the like. However, when the boiling point is very high and distillation cannot be performed, or solidification does not occur, unreacted acid halogen is obtained by concentration. The agent may be removed and used in the next step.

  The compound represented by the general formula (VI) is preferably produced through a step of reacting the compound represented by the general formula (VII) with the compound represented by the general formula (VIII). Details will be described below.

<Step of obtaining a compound represented by the general formula (VI) by reacting a compound represented by the general formula (VII) with a compound represented by the general formula (VIII)>

In the general formula (VII-2), ^{R 1} and ^{R 2} are the same meanings as ^{R 1} and ^{R 2} in the general formula (IV).

In the general formula (VIII), ^{R 3} and ^{L 1} have the same meanings as ^{R 3} and ^{L 1} in the general formula (VI). L ² represents a leaving group. The leaving group represented by L ² is the same as the leaving group represented by L ^1, but is preferably a leaving group that has the same or higher leaving ability as L ¹ . Specifically, when L ¹ is a chlorine atom, L ² is preferably a chlorine atom, a bromine atom, an iodine atom, or a sulfonyloxy group, more preferably a bromine atom or an iodine atom, Most preferably it is. When L ¹ is a bromine atom, L ² is preferably a bromine atom, an iodine atom, or a sulfonyloxy group, more preferably a bromine atom or an iodine atom, and most preferably an iodine atom. When L ² is an iodine atom, L ¹ is preferably an iodine atom. When L ² is a sulfonate group, L ² is preferably a sulfonate group.

Among the combinations of L ¹ and L ^2, a combination in which L ¹ is a chlorine atom and L ² is an iodine atom is most preferable from the viewpoint of selectivity.

  In the case of reacting the compound represented by the general formula (VII) and the compound represented by the general formula (VIII), the compound represented by the general formula (VII) is reacted with the base compound to produce the general formula (VII-2). It is preferable to generate an enolate represented by the formula (I) as an intermediate and then react with the compound represented by the general formula (VIII).

In the general formula (VII-2), ^{R 1} and ^{R 2} are the same meanings as ^{R 1} and ^{R 2} in the general formula (IV).

  As the base for generating the enolate represented by the general formula (VII-2), a known base can be used. For example, lithium diisopropylamide, potassium hexamethyldisilazide, metal hydride (for example, lithium hydride, Sodium hydride, potassium hydride, etc.), metal hydroxide (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), metal alkoxide (eg, sodium methoxide, sodium ethoxide, sodium tert-butoxide, lithium) tert-butoxide, potassium tert-butoxide, etc.), potassium hydride, potassium hexamethyldisilazide and potassium tert-butoxide are particularly preferred, and potassium tert-butoxide is most preferred. One type of these bases may be used, or two or more types may be mixed and used.

The amount of the base used is preferably 1 to 3 mol, more preferably 1 to 2 mol, and more preferably 1.05 to 1.5 mol based on 1 mol of the compound represented by the general formula (VII). Is most preferred. The reaction temperature is preferably −40 to 30 ° C., more preferably −40 to 20 ° C., and most preferably −20 to 20 ° C. By being in this temperature range, the cooling cost can be suppressed, and the manufacturing cost can be reduced. Further, the enolate represented by the general formula (VII-2) is hardly decomposed, and the yield can be improved.
The reaction time is preferably 0.1 to 5 hours, more preferably 0.5 to 3 hours, and most preferably 0.5 to 2 hours.

The compound represented by the general formula (VIII) to be reacted with the compound represented by the general formula (VII) is preferably used in an amount of 1 to 10 mol per 1 mol of the compound represented by the general formula (VII). It is more preferable to use ˜5 mol, and most preferable to use 1 to 2 mol. The reaction temperature is preferably −40 to 30 ° C., more preferably −40 to 20 ° C., and most preferably −20 to 10 ° C. from the viewpoint of productivity. By setting this temperature range, the reactivity is high and the reaction selectivity is high, so that the yield of the target product is high and the productivity is good.
The reaction time is preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours, and most preferably 0.5 to 3 hours.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.
Example 1

  Under a nitrogen stream, 600 ml of THF was added to 61.71 g (0.55 mol) of potassium tert-butoxide in the reactor, and the internal temperature was cooled to −10 ° C. To the reaction solution, 50 g (0.5 mol) of (A1) having the following structure was added dropwise over 20 minutes. Thereafter, after stirring at 0 ° C. for 15 minutes, 112.4 g (0.55 mol) of 1-chloro-3-iodopropane was added dropwise over 15 minutes, followed by stirring at −10 ° C. for 3 hours. After completion of the reaction, 1 L of water and 300 mL of ethyl acetate were added to carry out a liquid separation operation. The organic layer was concentrated and distilled under reduced pressure to obtain 83 g (0.47 mol, yield 85%) of exemplary compound (III-1) having the following structure. Subsequently, 20 g (113 mmol) of exemplary compound (III-1) having the following structure, 192 mL of t-butanol, and 40 mL of 2-methyl-2-butene were added to the reactor, and the internal temperature was cooled to 0 ° C. A solution obtained by dissolving 79.3 g (509 mmol) of sodium dihydrogen phosphite dihydrate in 160 mL of water was added to the reaction solution. Subsequently, a solution obtained by dissolving 46 g (509 mmol) of sodium chlorite in 160 mL of water was dropped over 30 minutes, and then the temperature was raised to room temperature and stirred for 2 hours. After completion of the reaction, 1 L of water, 300 mL of ethyl acetate, and 40 g of sodium chloride were added to carry out a liquid separation operation. The organic layer was washed with an aqueous sodium thiosulfate solution and a saturated aqueous sodium chloride solution. By concentrating the organic layer under reduced pressure, 21 g of an unpurified product of exemplary compound (II-1) having the following structure was obtained. Subsequently, 46.3 g (389 mmol) of thionyl chloride was added to the reactor equipped with a reflux ring and a basic trap. After making the inside of a reactor nitrogen atmosphere, compound (II-1) 50g (259 mmol) was dripped over 30 minutes. Then, it heated until it became internal temperature 30 degreeC, and stirred for 2 hours. After completion of the reaction, thionyl chloride was distilled off under reduced pressure and distilled under reduced pressure to obtain 51.9 g (246 mmol) of Exemplified Compound (I-1) having the following structure, yield 81% based on (A1). . The purity as measured by gas chromatography was 98%.

A synthesis scheme is shown below.

The compound data of exemplary compounds (III-1), (II-1) and (I-1) obtained in each step were measured using ¹ HNMR (Gemini-300 manufactured by Varian). The results are as follows.

The compound data of exemplary compound (III-1) having the above structure is shown below.
¹ H NMR (300 MHz, CDCl ₃ ): δ 0.80 (6H, t), 1.52-1.64 (8H, m), 3.51-3.53 (2H, m), 9.42 (1H , S)
Boiling point 73 ° C / 15mmHg

The compound data of exemplary compound (II-1) having the above structure is shown below.
¹ H NMR (300 MHz, CDCl ₃ ): δ 0.84 (6H, t), 1.58-1.71 (8H, m), 3.51-3.56 (2H, m)

The compound data of exemplary compound (I-1) having the above structure is shown below.
¹ H NMR (300 MHz, CDCl ₃ ): δ 0.87 (6H, t), 1.65 to 1.84 (8H, m), 3.55 (2H, t)

(Examples 2 to 7)
The reaction was performed at the temperature described in Table 4 below, and the same operation as in Example 1 was performed except that the types were changed to the oxidizing agent and acid halogenating agent described in Table 4 below, respectively.

(Examples 8 to 10)
It replaced with the raw material (A1), and performed the same operation as Example 1 except having used the following structure (A2), (A3), and (A4) as a raw material, respectively. In addition, the -Es' value of the substituent in the following structure (A3) is 1.5 or more.

As a result, exemplary compounds (I-29), (I-30) and (I-7) were obtained, respectively.
The compound data of the obtained exemplary compounds (I-29), (I-30) and (I-7) are as follows.
The compound data of (I-29) is shown below.
Exemplary compound (I-29): ¹ H NMR (300 MHz, CDCl ₃ ): δ 0.82 (3H, t), 0.87 (3H, t), 1.65 to 1.84 (12H, m), 3 .54 (2H, t)
The compound data of exemplary compound (I-30) are shown below.
Exemplary compound (I-30): δ 0.95 (3H, t), 1.65 to 1.84 (6H, m), 3.56 (2H, t), 5.21 (1H, d), 5. 35 (1H, d), 5.92 (1H, m)
The compound data of exemplary compound (I-7) are shown below.
Illustrative compound (I-7): ¹ H NMR (300 MHz, CDCl ₃ ): δ 0.86 (6H, t), 1.63-1.85 (12H, m), 3.53 (2H, t)
(Comparative Example 1)

  Under a nitrogen stream, 100 g (1.0 mol) of diisopropylamine and 500 mL of tetrahydrofuran were added and cooled to −10 ° C. Next, 356 mL (0.92 mol) of a 2.6 mol / l butyllithium / hexane solution was dropped over 1 hour to prepare lithium diisopropylamide in the reaction system. Next, 123 g (0.85 mol) of (A7) having the following structure was added dropwise over 1 hour at −10 to 10 ° C. (temperature of enolization). After stirring for 1 hour, 198.0 g (1.3 mol) of 3-chloro-1-bromopropane was added dropwise over 2 hours, and the reaction temperature was controlled between −10 to 10 ° C. (alkylation temperature). After stirring at 0 ° C. for 1 hour, 300 mL of water was added and a liquid separation operation was performed. Further, the oil layer obtained with an aqueous solution of concentrated hydrochloric acid 100 mL / water 200 mL was washed twice, and transport was washed once with a saturated aqueous sodium hydrogen carbonate solution. The obtained oil layer was dried over magnesium sulfate and concentrated to obtain a compound represented by (III-A) having the following structure. To this, 112 g (1.0 mol) of a 50 mass% potassium hydroxide aqueous solution and 500 g of ethanol were added and heated at an external temperature of 80 ° C. for 4 hours. After concentrating the solvent, liquid separation was performed with 500 mL of ethyl acetate / 1500 mL of hydrochloric acid, and after concentrating the oil layer, 154.7 g (1.3 mol) of thionyl chloride was added and heated at 50 ° C. for 2 hours. This was distilled under reduced pressure (boiling point 90 ° C./1 mmHg) to obtain 118.4 g (0.56 mol) of the compound represented by the exemplified compound (I-1) having the following structure, and a yield of 66% based on (A7). It was. The purity by gas chromatography measurement was 72%, and 20% was a compound (I-1) ′ having the following structure, which was deHCled.

A synthesis scheme is shown below.

(Comparative Example 2)

  The same operation as in Comparative Example 1 was performed to obtain a compound represented by the structure (III-A). To this, 20 g (0.1 mol) of trimethylsilyl iodide, 50 g of water, and 500 g of ethanol were added and heated at an external temperature of 80 ° C. It took 144 hours to complete the reaction. After concentrating the solvent, liquid separation was performed with 500 mL of ethyl acetate / 1500 mL of hydrochloric acid, and after concentrating the oil layer, 154.7 g (1.3 mol) of thionyl chloride was added and heated at 50 ° C. for 2 hours. This was distilled under reduced pressure (boiling point 90 ° C./1 mmHg) to obtain 92.9 g (0.44 mol) of Example Compound (I-1) having the following structure and a yield of 52% based on (A7). The purity as measured by gas chromatography was 92%.

A synthesis scheme is shown below.

  From the above results, by using the production method of the present invention, an acid halide having a leaving group and a bulky group useful as a synthesis intermediate of a functional compound can be obtained in high yield and / or high purity. It became clear that it can be manufactured with. Moreover, according to the said method, it became clear that the acid halide which has a leaving group and a bulky group which are useful as a synthetic intermediate of a functional compound can be provided.

Claims (8)

A step of obtaining a compound represented by the following general formula (II) by reacting a compound represented by the following general formula (III) with an oxidizing agent, and converting the compound represented by the following general formula (II) into an acid A step of obtaining a compound represented by the following general formula (I) by reacting with a halogenating agent, and a method for producing an acid halide.

In the general formula (I), A represents a divalent linking group obtained by removing one atom from a monovalent substituent having a steric parameter -Es' value of 1.5 or more. X ¹ represents a halogen atom. L ¹ represents a leaving group.

In formula (II), A and ^{L 1} are the same meanings as A and ^{L 1} in the general formula (I).

In general formula (III), A and L ¹ are respectively synonymous with A and L ¹ in general formula (I). The compound represented by the general formula (I) is a compound represented by the following general formula (IV), and the compound represented by the general formula (II) is represented by the following general formula (V). The method for producing an acid halide according to claim 1, wherein the compound is a compound represented by the general formula (III), and is a compound represented by the following general formula (VI).

In general formula (IV), R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. R ³ represents an alkylene group. X ¹ and ^{L 1} are the same respectively as ^{X 1} and ^{L 1} in the general formula (I).

In the general formula ^(V), R ^1, R 2, ^{R 3} and ^{L 1} are respectively ^{R 1,} R 2, ^{R 3} and ^{L 1} synonymous in the general formula (IV).

In the general formula ^(VI), R ^1, R 2, ^{R 3} and ^{L 1} are respectively ^{R 1,} R 2, ^{R 3} and ^{L 1} synonymous in the general formula (IV). And a step of obtaining a compound represented by the general formula (VI) by reacting a compound represented by the following general formula (VII) with a compound represented by the following general formula (VIII). Item 3. A process for producing an acid halide according to Item 2.

In the general formula (VII), ^{R 1} and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in the general formula (IV).

In the general formula (VIII), ^{R 3} and ^{L 1} are the same meanings as ^{R 3} and ^{L 1} in the general formula (IV). L ² represents a leaving group.   The reaction temperature of the step of obtaining the compound represented by the general formula (VI) by reacting the compound represented by the general formula (VII) with the compound represented by the general formula (VIII) is- The method for producing an acid halide according to claim 3, wherein the temperature is from 20 ° C to 10 ° C.   The oxidant is an oxidant selected from the group consisting of potassium permanganate, hydrogen peroxide, sodium chlorite, or a mixture of two or more thereof. The manufacturing method of the acid halide of description.   The method for producing an acid halide according to any one of claims 1 to 5, wherein the acid halogenating agent is an acid halogenating agent selected from the group consisting of thionyl chloride, phosphoryl chloride or oxalyl chloride. The compound represented with the following general formula (I) obtained by the manufacturing method as described in any one of Claims 1-6.

In the general formula (I), A represents a divalent linking group obtained by removing one atom from a monovalent substituent having a steric parameter -Es' value of 1.5 or more. X ¹ represents a halogen atom. L ¹ represents a leaving group. The compound represented by the following general formula (IV) obtained by the manufacturing method as described in any one of Claims 2-6.

In general formula (IV), R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. R ³ represents an alkylene group. X ¹ and ^{L 1} are the same respectively as ^{X 1} and ^{L 1} in the general formula (I).