JP4299521B2 - Phthalic anhydride compound having ethynyl group and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel aromatic acetylene compound (phthalic anhydride compound having an ethynyl group) useful as a thermosetting resin, a liquid crystal material, a nonlinear optical material, a photographic additive, or a synthetic intermediate thereof, and a method for producing the same. .
[0002]
[Prior art]
As for the synthesis of aromatic acetylene compounds, a coupling reaction between an aromatic halogen compound and an acetylene compound using a palladium catalyst has been developed in recent years. Have been widely used (for example, Non-Patent Document 1, Non-Patent Document 2, Patent Document 2, etc.).
On the other hand, Non-Patent Document 3 describes the synthesis of the following compound (5) by the following reaction route using the method of Sugawara-Sonogami et al.
[0003]
[Chemical formula 5]
[0004]
However, in order to synthesize the ethynyl-substituted phthalic anhydride compound, which is the above compound (5), dimethyl ester of phthalic acid which is stable under the above coupling reaction conditions is used. Since 3) is led to phthalic anhydride after being hydrolyzed, there are many reaction steps, and there are disadvantages in terms of efficiency and production cost when performing large-scale synthesis. In addition, in the above reaction, in the case of a compound having an unstable group other than the coupling site, a decrease in yield was expected.
On the other hand, as thermosetting resins, liquid crystal materials, nonlinear optical materials, and photographic additives, development of compounds exhibiting superior performance or intermediates for synthesizing these compounds is desired. In particular, in thermosetting resins, polyimide resins are used, and development of resin raw materials with excellent thermosetting properties is desired.
[0005]
[Patent Document 1]
JP-A-10-114691 [Non-Patent Document 1]
Tetrahedron Lett. 1975, 4467, J.A. Org. Chem. , 59, 5818 (1994)
[Non-Patent Document 2]
J. et al. Org. Chem. , 59, 5818 (1994)
[Non-Patent Document 3]
J. et al. Org. Chem. , 48, 5135 (1983)
[0006]
[Problems to be solved by the invention]
The object of the invention is to provide a novel aromatic acetylene compound (phthalic anhydride compound having an ethynyl group) useful as a thermosetting resin, a liquid crystal material, a nonlinear optical material, a photographic additive, or a synthetic intermediate thereof. Furthermore, the present invention provides a production method for producing a phthalic anhydride compound having an ethynyl group with high efficiency and low cost.
[0007]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above object can be achieved by the following compounds and production methods. That is,
(1) A compound represented by the following general formula (I).
[0008]
[Chemical 6]
[0009]
In the general formula (I), R ₁ represents a substituent selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a silyloxy group, an alkylthio group, an arylthio group, a phosphino group, and a silyl group , n ₁ represents an integer of 0 to 3. When n ₁ is 2 or 3, the plurality of R ₁ may be the same as or different from each other. R ₂ represents an alkyl group having a hydroxy group at the α-position or a group represented by the following general formula (II).
[0010]
[Chemical 7]
[0011]
In the general formula (II), R ₃ , R ₄ and R ₅ each independently represents an alkyl group or an aryl group.
(2) The compound represented by the general formula (I) according to (1), wherein R ₁ is a hydrogen atom or a substituent selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, and a silyl group.
(3) The compound represented by the general formula (I) according to (2), wherein R ₁ is a hydrogen atom, an alkyl group, or an aryl group.
(4) The compound represented by the general formula (I) according to any one of (1) to (3), wherein n ₁ is 0, 1, or 2.
(5) The compound represented by the general formula (I) according to (4), wherein n ₁ is 0 or 1.
(6) The compound represented by the general formula (I) according to (5), wherein n ₁ is 0.
(7) A method for producing a compound represented by the following general formula (I), comprising using a compound represented by the following general formula (III) and a compound represented by the following general formula (IV).
[0012]
[Chemical 8]
[0013]
In the general formulas (I) and (III), R ₁ is a substituent selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a silyloxy group, an alkylthio group, an arylthio group, a phosphino group, and a silyl group. N ₁ represents an integer of 0 to 3. When n ₁ is 2 or 3, the plurality of R ₁ may be the same as or different from each other. In general formula (III), X represents a halogen atom. In the general formulas (I) and (IV), R ₂ represents an alkyl group having a hydroxy group at the α-position or a group represented by the following general formula (II).
[0014]
[Chemical 9]
[0015]
In the general formula (II), R ₃ , R ₄ and R ₅ each independently represents an alkyl group or an aryl group.
(8) The production method according to (7), wherein R ₁ is a hydrogen atom or a substituent selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, and a silyl group.
(9) The production method according to (8), wherein R ₁ is a hydrogen atom, an alkyl group, or an aryl group.
(10) The production method according to any one of (7) to (9), wherein n ₁ is 0, 1, or 2.
(11) The production method according to (10), wherein n ₁ is 0 or 1.
(12) The production method according to (11), wherein n ₁ is 0.
( 13 ) The production method according to any one of ( 7) to (12) , wherein the reaction is carried out in the presence of a palladium catalyst, a copper salt, and a base.
( 14 ) The method according to ( 13 ), wherein the base is an organic base.
(15) The process according to you comprises reacting in the presence of a halogen ion releasable compound (7) to (14).
( 16 ) The method according to any one of (7) to (15) , wherein a non-aqueous reaction medium is used.
( 17 ) The production method according to any one of ( 7 ) to ( 16 ), wherein X in the general formula (III) is a bromine atom or a chlorine atom.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
First, the compound represented by the general formula (I) of the present invention will be described.
[0017]
In the general formula (I), examples of the substituent represented by R ₁ represents A alkyl group [a straight chain, branched, or cyclic, substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [2,2,1] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl moiety in a substituent described below (for example, an alkyl group of an alkylthio group) also represents such an alkyl group. ],
[0018]
Ali Lumpur group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p- tolyl, naphthyl, m- chlorophenyl, o- hexadecanoylaminophenyl group), an alkoxy group (preferably, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably having 6 to 30 carbon atoms) Substituted or unsubstituted aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy),
[0019]
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy ),
[0021]
Al Kiruchio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n- hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as , Phenylthio, p-chlorophenylthio, m-methoxyphenylthio ),
[0023]
Phosphino groups (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, e.g., dimethylphosphino, diphenylphosphino, methylphenoxy phosphino) and silyl groups (preferably, from 3 to 30 carbon atoms a substituted or unsubstituted silyl group, e.g., trimethylsilyl, t- butyl dimethylsilyl, phenyldimethylsilyl) and the like.
[0024]
Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.
[0025]
Substituents have preferred as R ₁ is A alkyl group, an aryl group, an alkoxy group or a silyl group, more preferably an alkyl group or an aryl group.
[0026]
n ₁ represents an integer of 0 to 3, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0.
When n ₁ is 2 or 3, the plurality of R ₁ may be the same as or different from each other. Furthermore, when n ₁ is 2 or 3, a plurality of R ₁ may be bonded to each other to form a ring structure (specific examples include I-6 and I-19 shown below).
[0027]
R ₂ is an alkyl group having a hydroxy group at the α-position (for example, 1-methyl-1-hydroxyethyl, hydroxymethyl, 1-hydroxyethyl, 1-phenyl-1-hydroxyethyl), or represented by the general formula (II). Represents a group. Of these, R ₂ is preferably an alkyl group having a hydroxy group at the α-position. The alkyl group may have a substituent in addition to the α-position hydroxy group. Examples of the substituent include the same as those for R ₁ described above. Preferred substituents are an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, and a halogen atom, more preferably an alkyl group, an aryl group, and a halogen atom, and still more preferably an alkyl group and an aryl group.
In the general formula (II), R ₃ , R ₄ and R ₅ each independently represents an alkyl group (eg, methyl, ethyl, butyl) or an aryl group (eg, phenyl). R ₃ , R ₄ and R ₅ are all preferably alkyl groups, and most preferably all are methyl groups.
[0028]
R ₂ is preferably an alkyl group having a total number of carbon atoms of 1 to 5 and having a hydroxy group at the α-position or a trialkylsilyl group having a total number of carbon atoms of 6 or less (ie 3 to 6), A 1-methyl-1-hydroxyethyl group or a trimethylsilyl group is preferred, and a 1-methyl-1-hydroxyethyl group is most preferred.
[0029]
Specific examples of the compound represented by the general formula (I) of the present invention are shown below, but the compound of the present invention is not limited thereto.
[0030]
[Chemical Formula 10]
[0031]
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[0032]
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[0033]
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[0034]
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[0035]
Next, the manufacturing method of the compound represented by the general formula (I) of the present invention will be described in detail.
The compound represented by the general formula (I) of the present invention uses (that is, reacts) the compound represented by the general formula (III) and the compound represented by the general formula (IV). Features.
Here, the compound represented by the general formula (III) and the compound represented by the general formula (IV) will be described first.
In general formula (III), R ₁ and n ₁ are each the same meaning as R ₁ and n ₁ in the general formula (I), the preferable range is also the same.
[0036]
X in the general formula (III) represents a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom, and most preferably a bromine atom.
[0037]
R ₂ in the general formula (IV) has the same meaning as R ₂ in formula (I), and preferred ranges are also the same.
[0038]
Specific examples of the compound represented by the general formula (III) are shown below, but the present invention is not limited thereto.
[0039]
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[0040]
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[0041]
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[0042]
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[0043]
Next, a method for producing a compound represented by the general formula (I) as a raw material using the compound represented by the general formula (III) and the compound represented by the general formula (IV) will be described.
The production method of the present invention is characterized in that a halogen-substituted phthalic anhydride is directly ethynylated to produce a phthalic anhydride substituted with an ethynyl group, and a production route.
[0044]
The compound represented by the general formula (IV) is used in an amount of 0.1 to 20 mol, preferably 0.5 to 5 mol, per 1 mol of the compound represented by the general formula (III).
[0045]
In the present invention, it is particularly preferable to use a reaction catalyst. As the catalyst, a palladium catalyst and a copper catalyst are used in combination.
As the palladium catalyst, a commercially available palladium compound such as zero-valent or divalent palladium metal or salt (including a complex) can be used, and these may be supported on activated carbon or the like. Preferred examples include palladium (0) carbon, palladium (II) acetate, palladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, tetrakis (triphenylphosphine) palladium (0), and the like. Can do. Of these, bis (triphenylphosphine) palladium (II) chloride is particularly preferably used. The palladium catalyst is 1 × 10 ⁻⁶ to 10 mol, preferably 1 × 10 ⁻⁵ to 1 mol, more preferably 1 × 10 ⁻⁴ × 10 ^{− to} 1 mol of the compound represented by the general formula (III). ¹ mole is used.
[0046]
As the copper salt, a monovalent or divalent copper salt can be used, and a monovalent copper salt is preferably used. Particularly preferably, copper iodide is used. The copper salt is preferably used in an amount of 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol per 1 mol of the compound represented by the general formula (III).
[0047]
In the present invention, the reaction can also be carried out by adding a phosphine compound (trivalent phosphorus compound). Of these, triphenylphosphine is most often used, but trivalent phosphorus compounds having two phosphorus atoms in the molecule can also be used. The phosphine compound is preferably used in an amount of 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol with respect to 1 mol of the compound represented by the general formula (III).
[0048]
In the present invention, it is preferable to use a base in addition to the catalyst.
Examples of the base include sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, etc. In addition, organic bases such as triethylamine, diethylamine, piperidine, pyrrolidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) and the like can be used. Preferably, an organic base is used, particularly triethylamine or diethylamine. The base is used in an amount of 1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the compound represented by the general formula (III). The organic base is preferably used as a reaction solvent described later.
[0049]
It is also preferable to add a halogen ion releasable compound described in JP-A-10-114691. Halogen ion releasable compounds are represented as M ⁺ X-.
Here, M represents an alkali metal (for example, lithium, sodium, potassium), or a hydrogen atom, an alkyl group (for example, methyl, ethyl, propyl, butylbenzyl) or an aryl group (for example, phenyl) to a nitrogen atom, a sulfur atom or Represents a compound residue having a phosphorus atom, preferably an alkali metal, or a compound residue having a hydrogen atom or an alkyl group on a nitrogen atom or a phosphorus atom, more preferably an alkyl group on a nitrogen atom or a phosphorus atom. And particularly preferably a compound residue having an alkyl group on the nitrogen atom. X represents a compound residue on the halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom.
[0050]
Examples of the compound capable of releasing halogen ions include alkali metal salts (for example, LiBr, NaCl, KF), tetraalkylammonium halides (for example, triethylammonium chloride, diethylbenzylammonium bromide, tetrabutylammonium bromide, etc.), phosphonium halides ( For example, tetraphosphonium bromide), preferably tetraalkylammonium halide or phosphonium halide, and more preferably tetraalkylammonium halide.
More specifically preferred compounds include tetraalkylammonium chloride, tetraalkylammonium bromide, tetraalkylphosphonium chloride or tetraalkylphosphonium bromide.
The compound capable of releasing halogen ions is used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of the compound represented by the general formula (III).
[0051]
The reaction solvent is preferably a non-aqueous solvent, more preferably an aromatic hydrocarbon solvent (eg toluene), a nitrile solvent (eg acetonitrile), an amide solvent (eg N, N-dimethylacetamide), an ether solvent (eg THF), amine solvents (for example, triethylamine, pyrrolidine, diethylaminopiperidine, pyridine) and the like are used.
In the present invention, it is more preferable to use an amine solvent, and an organic base such as triethylamine, diethylaminepiperidine, pyrrolidine or the like can also be used. In this case, an amine solvent and another solvent can be used in combination, and examples of these solvents include solvents other than the above amine solvents, but only amine solvents are preferable.
[0052]
The reaction temperature is 0 to 150 ° C, preferably 20 to 130 ° C, more preferably 20 to 100 ° C.
[0053]
【Example】
Next, the present invention will be described in more detail based on examples.
Example 1.
Exemplified compound (I-1) was synthesized based on the following formula.
[0054]
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[0055]
Compound (III-1) 114 g, compound (11) 50.5 g, triphenylphosphine 0.45 g, triethylamine 450 ml, bistriphenylphosphine palladium chloride (II) 0.14 g, copper chloride (I) 1. 33 g was added and heated to reflux for 4 hours. Subsequently, the mixture was cooled to room temperature and concentrated by a rotary evaporator, and extracted by adding 1300 ml of ethyl acetate and 1000 ml of water. The obtained ethyl acetate layer was washed 4 times with a mixed aqueous solution of 100 ml of saturated brine and 600 ml of water, dried over anhydrous magnesium sulfate, and concentrated on a rotary evaporator. A mixed solution consisting of 50 ml of ethyl acetate and 50 ml of hexane was added to the obtained residue to dissolve, and a mixed solution consisting of 80 ml of ethyl acetate and 600 ml of hexane was added dropwise thereto over 1 hour with stirring. After stirring for 3 hours, the mixture was allowed to stand for 12 hours, and the resulting crystals were filtered to obtain 43.7 g of the target exemplified compound (I-1) (yield 38%).
NMR (CDCl ₃ ): δ = 8.011 (d, J = 1.2 Hz, 1H), 7.956 (d, J = 8.1 Hz, 1H), 7.884 (dd, J = 1.2, 8.1 Hz, 1H), 2.085 (brs, 1H), 1.656 (s, 6H)
Melting point: 130-131 ° C
[0056]
Example 2
Exemplified compound (I-8) was synthesized based on the following formula.
[0057]
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[0058]
In a three-necked flask, 114 g of compound (III-1), 33.6 g of propargyl alcohol, 0.45 g of triphenylphosphine, 450 ml of triethylamine, 0.14 g of bistriphenylphosphine palladium chloride (II), 1.33 g of copper (I) chloride, 80.6 g of tetrabutylammonium bromide was added and heated to reflux for 4 hours. Subsequently, the mixture was cooled to room temperature and concentrated by a rotary evaporator, and extracted by adding 1300 ml of ethyl acetate and 1000 ml of water. The obtained ethyl acetate layer was washed four times with a mixed aqueous solution of 100 ml of saturated brine and 600 ml of water, dried over anhydrous magnesium sulfate, and concentrated on a rotary evaporator. A mixed solution consisting of 50 ml of ethyl acetate and 50 ml of hexane was added to the obtained residue and dissolved, and a mixed solution consisting of 80 ml of ethyl acetate and 500 ml of hexane was added dropwise thereto over 1 hour with stirring. The mixture was stirred for 3 hours as it was, then allowed to stand for 12 hours, and the obtained crystals were filtered to obtain 31.3 g of the target exemplified compound (I-8) (yield 31%).
[0059]
【The invention's effect】
According to the present invention, an aromatic acetylene compound can be easily and efficiently produced directly from halophthalic anhydride.

Claims (17)

Compound represented by the following general formula (I) :
(In General Formula (I), R ₁ represents a substituent selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a silyloxy group, an alkylthio group, an arylthio group, a phosphino group, and a silyl group ; n ₁ represents an integer of 0 to 3. When n ₁ is 2 or 3, a plurality of R ₁ may be the same or different from each other, R ₂ is an alkyl group having a hydroxy group at the α-position, or the following general formula Represents a group represented by (II) );
(In the general formula (II), R ₃ , R ₄ and R ₅ each independently represents an alkyl group or an aryl group. ) R ₁ Is a substituent selected from the group consisting of an alkyl group, an aryl group, an alkoxy group and a silyl group, The compound represented by formula (I) according to claim 1. R ₁ The compound represented by the general formula (I) according to claim 2, wherein is an alkyl group or an aryl group. n ₁ Is 0, 1, or 2. The compound represented by formula (I) according to any one of claims 1 to 3. n ₁ The compound represented by the general formula (I) according to claim 4, wherein is 0 or 1. n ₁ Is 0, The compound represented by general formula (I) of Claim 5. A method for producing a compound represented by the following general formula (I), which comprises using a compound represented by the following general formula (III) and a compound represented by the following general formula (IV) :
(In the general formulas (I) and (III), R ₁ is a substituent selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, silyloxy groups, alkylthio groups, arylthio groups, phosphino groups, and silyl groups. Represents a group, and n ₁ represents an integer of 0 to 3. When n ₁ is 2 or 3, a plurality of R ₁ may be the same or different from each other, in formula (III), X represents a halogen atom . formula (I), in (IV), _{R 2} represents a group represented by alkyl group or a group represented by the general formula having a hydroxyl group at position α (II)).;
(In the general formula (II), R ₃ , R ₄ and R ₅ each independently represents an alkyl group or an aryl group. ) R ₁ Is a substituent selected from the group consisting of an alkyl group, an aryl group, an alkoxy group and a silyl group. R ₁ The production method according to claim 8, wherein is an alkyl group or an aryl group. n ₁ Is 0, 1, or 2. The manufacturing method of any one of Claims 7-9. n ₁ The manufacturing method according to claim 10, wherein is 0 or 1. n ₁ The manufacturing method according to claim 11, wherein It reacts in presence of a palladium catalyst, copper salt, and a base, The manufacturing method of any one of Claims 7-12 characterized by the above-mentioned. The production method according to claim 13 , wherein the base is an organic base. The method according to any one of claims 7 to 14 , wherein the reaction is carried out in the presence of a compound capable of releasing a halogen ion. The production method according to claim 7 , wherein a non-aqueous reaction medium is used. The production method according to any one of claims 7 to 16, wherein X in the general formula (III) is a bromine atom or a chlorine atom.