JPH11246540A - Oxetane group-containing calix(4)resorcin arene derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new derivative having extremely enriched reactivity and extremely excellent as a raw material of a functional material while maintaining heat resistance intrinsically possessed by calix[4]resorcin arene. SOLUTION: This derivative is expressed by formula I (R1 is H or a 1-17C alkyl; R2 is H or a 1-6C alkyl), e.g. methylcalix[4]resorcin arene. The derivative is obtained by reacting a calix[4]resorcin arene of formula II with a compound of formula III (R3 is a 1-4C alkyl) (e.g. 3-ethyl-3-oxetanylmethyltosylate) in a reaction solvent (e.g. N,N-dimethylformamide) in the presence of a quaternary onium salt at a temp. of 50-150 deg.C for 1-50 hrs.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound represented by the following general formula (I):
An oxetane group-containing calix [4] resorcinarene derivative represented by the formula:

[0002]

Embedded image (In the formula, R ₁ represents hydrogen or an alkyl group which may have a C ₁ -C ₁₇ branch, and R ₂ represents hydrogen or an alkyl group which may have a C ₁ -C ₆ branch.)

[0003]

2. Description of the Related Art Calixarenes are cyclic oligomers in which a plurality of phenol units are linked via a methylene group, and occupy an important position in the study of host / guest chemistry. Because of its high heat resistance, various uses for a new functional material have been studied. For research on calixarenes, Nishikubo et al. Reported on the synthesis, photoreactivity, and heat resistance of photo-cured p-alkyl-calixarenes having a (meth) acryloyl group (The 45th Society of Polymer Science, Japan) Annual convention, 11Pf06
8), also reported by Nishikubo et al. On the synthesis of p-methyl-calixarene having vinyloxy, propargyl and 1-propenyl groups and its photocationic polymerization (46th Annual Meeting of the Society of Polymer Science, 111E18). is there. An acetylated product of p-methyl-calixarene and a film formed from the acetylated product are reported in Japanese Patent Publication No. 23340/1995, and OH of a phenol group useful for selective separation and extraction of metal ions is disclosed. A novel calixarene derivative in which a hydrogen atom of a group is substituted by a specific substituent is disclosed in
No. 127561. On the other hand, calix [4] resorcinarene derivative, which is a cyclic oligomer in which four resorcinols of dihydric phenol are bonded using aldehydes, is considered to be an OH derived from resorcinol.
Substituted hydrogen atoms of specific groups with specific substituents have been proposed as surface modifiers and detergents (JP-A-7-25).
2177, and JP-A-8-245474).

[0004]

Research on calixarene as a functional material has only just begun, and at present the calixarene derivatives that can meet the needs of various markets have not yet been provided. .

[0005]

Means for Solving the Problems The present inventors have conducted various studies to create a novel reactive calix [4] resorcinarene derivative. As a result, the present inventors have found that a reactive oxetane group containing a reactive oxetane group is contained. The present inventors have found that calix [4] resorcinarene derivative is extremely reactive and extremely excellent as a raw material for functional materials, while maintaining the heat resistance inherent in calix [4] resorcinarene. It has been completed. That is, the present invention relates to the following general formula (I)

[0006]

Embedded image (Wherein, R ₁ and R ₂ have the same meanings as described above). The present invention does not provide an oxetane group-containing calix [4] resorcinarene derivative and a method for producing the same.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The oxetane group-containing calix [4] resorcinarene derivative represented by the above general formula (I) is represented by the following general formula (II)

[0008]

Embedded image (Wherein R ₁ represents hydrogen or an alkyl group which may have a C ₁ -C ₁₇ branch) and calix [4] resorcinarene represented by the following general formula (III)

[0009]

Embedded image Wherein R ₂ represents hydrogen or an alkyl group which may have a C ₁ -C ₆ branch, and R ₃ represents an alkyl group which may have a C ₁ -C ₄ branch, a phenyl group or p -Representing a tolyl group) in a solvent in the presence of a quaternary onium salt at a temperature of 50 to 150 ° C for 1 to 50 hours.

The calix [4] resorcinarene represented by the above general formula (II) is a known compound, and its synthesis method is described in Journal of American Chemical Society, 111,
14, 5397 (1989). As the substituent R ₁ of the calix [4] resorcinol arene represented by the general formula (II), in addition to a hydrogen atom, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n
-Pentyl group, isopentyl group, sec-amyl group, t
ert-amyl group, neopentyl group, n-hexyl group,
Isohexyl group, n-heptyl group, n-octyl group, n
And a C ₁ -C ₁₇ alkyl group which may have a branch such as a nonyl group. Among them, R ₁ is preferably hydrogen, a methyl group, an ethyl group, or an n-propyl group.

The compound represented by the general formula (III) is Botij
a Can be synthesized according to the method disclosed in Spanish Patent No. 2079395 by Gonzalez et al. That is, 3-alkyl-3
-Hydroxymethyl oxetane with R ₃ SO ₂ Cl (where R
₃ represents a p-tolyl group or the like), and is easily synthesized by reacting a sulfonyl chloride compound represented by the formula (1) in an organic solvent at 0 ° C. to room temperature (25 ° C.) in the presence of a suitable basic substance such as pyridine. can do. The synthesis method is as follows.

[0012]

Embedded image

The general formula (II) synthesized by the above synthesis method
The compound represented by I) can be used after purification according to a conventional method or without purification. However, in general, it is preferable to use a product purified by an operation such as distillation under reduced pressure after concentration. As the substituent R ₂ of the compound represented by the general formula (III), in addition to a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
-Butyl group, isobutyl group, sec-butyl group, ter
t-butyl group, n-pentyl group, isopentyl group, se
c-amyl group, tert-amyl group, neopentyl group,
An optionally branched C ₁ -C ₆ alkyl group such as an n-hexyl group and an isohexyl group is exemplified. A methyl group or an ethyl group is exemplified as a preferable example. The substituent R ₃ of the compound has a branch such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. A C ₁ -C ₄ alkyl group, a phenyl group, p
-Tolyl group and the like. More preferably, a p-tolyl group is used.

The compound represented by the above general formula (III) is a compound wherein R ₂ is a methyl group and R ₃ is a p-tolyl group.
Methyl-3-oxetanyl methyl tosylate (hereinafter referred to as MO
MT), R ₂ is an ethyl group, and R ₃ is p
-Ethyl group 3-ethyl-3-oxetanylmethyl tosylate (hereinafter sometimes referred to as EOMT).

Examples of the solvent used for synthesizing the compound represented by the general formula (III) include aromatic organic solvents such as benzene, toluene and pyridine. The amount of these organic solvents to be used is not particularly limited, but may be a 3-alkyl-3-hydroxymethyloxetane and a compound of the formula R ₃ SO ₂
Assuming that the total amount (weight) of the sulfonyl compound represented by Cl (wherein R ₃ is the same as described above) is 1, the sulfonyl compound may be used at a ratio of 2 to 20 times (volume).

In synthesizing the compound represented by the general formula (III), it is preferable to use a basic substance.
Examples of the basic substance include inorganic basic substances such as ammonium hydroxide (aqueous ammonia), hydroxides of alkali metals such as KOH and NaOH, and organic basic substances such as triethylamine and pyridine. The basic substance may be used in an amount of 1.0 to 1.2 mol per 1 mol of the sulfonyl compound represented by the formula R ₃ SO ₂ Cl (where R ₃ is the same as above).

The amounts of the 3-alkyl-3-hydroxymethyloxetane and the sulfonyl compound represented by the formula R ₃ SO ₂ Cl (where R ₃ is the same as above) are usually in equimolar amounts. One may be used in excess. That is, 3
The above-mentioned sulfonyl compound may be used in a proportion of 0.9 to 1.1 mol per 1 mol of -alkyl-3-hydroxymethyloxetane. Usually, the reaction is carried out at 0 ° C. to room temperature (2
(5 ° C.) for 30 minutes to 10 hours. Stirring is not always essential, but it is better to stir in order to promote uniform reaction and promote the reaction.

The reaction of calix [4] resorcinarene represented by the above general formula (II) with the compound represented by the above general formula (III) is usually carried out in a solvent. As such a solvent, the calix [4] resorcinarene represented by the general formula (II) and the compound represented by the general formula (III) are uniformly reacted in a reaction solvent, and therefore, at a reaction temperature applied. At least a calix [4] resorcinarene represented by the above general formula (II) and / or a compound represented by the general formula (III) and a calix [ 4] Any substance having an action of dissolving or swelling the resorcinarene derivative and having no reactivity with these compounds can be used. Such solvents include:
Tetrahydrofuran (THF), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), N-methyl-2-pyrrolidone (NMP) And the like. Among them, DMF, DMAC, and NMP are preferably used. The above solvent is calix [4] represented by the general formula (II).
What is necessary is just to use 2 to 20 times by volume per 1 part by weight of the total amount of resorcin arene and the compound represented by the general formula (III). That is, calix [4] represented by the general formula (II)
The resorcinol arene and the compound represented by the general formula (III) may be used at a ratio of 2 to 20 ml per 1 g in total.

Calix [4] represented by the general formula (II)
The reaction between resorcin arene and the compound represented by the general formula (III) is usually performed in the presence of a basic substance. Such basic substances include NH ₄ OH (ammonia water), alkali metal hydroxides (KOH, NaOH, LiOH, etc.), alkaline earth metal hydroxides (Ca (OH) ₂ , Mg (OH)
₂ , Ba (OH) ₂ etc.). The amount of the basic substance used depends on the general formula (II
The compound represented by the general formula (III) may be used in an equimolar amount to the compound represented by the formula (I), but may be used in a slight excess.
It may be used within a range of 1.0 to 1.2 mol per mol. By using a basic substance, a sulfonic acid (R ₃ SO ₃ H) by-produced, for example, p-toluenesulfonic acid, can be easily separated from the desired product oxetane group-containing calix [4] resorcinarene derivative. This is for converting into a metal salt or an ammonium salt, and therefore is not necessarily essential for the present reaction.

Calix [4] represented by the general formula (II)
Examples of the quaternary onium salt used as a catalyst in the reaction between resorcin arene and the compound represented by the general formula (III) include a compound represented by the following general formula (IV).

[0021]

Embedded image (Wherein, R _{4 to} R ₁₀ may be the same or different from each other, and represent a hydrogen atom, a hydroxyalkyl group, an alkyl group,
Represents an aryl group or an aralkyl group, and when these are an alkyl group or an aralkyl group,
Up to 30 linear, branched or cyclic hydrocarbon groups. M ₁ represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom, M ₂ represents an oxygen atom, a sulfur atom, a selenium atom or a tin atom, and M ₃ represents an iodine atom. And X represents a monovalent anion selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxide, a carbonate group, a bicarbonate group, a dihydrogen phosphate group and a bisulfate group). Specifically, in the general formula (IV), an ammonium compound when M ₁ is a nitrogen atom, a phosphonium compound when M ₁ is a phosphorus atom,
Arsonium compound when M ₁ is an arsenic atom, stibonium compound when M ₁ is an antimony atom, M ₂
An oxonium compound when is an oxygen atom, a sulfonium compound when M ₂ is a sulfur atom, a selenonium compound when M ₂ is a selenium atom, a stannonium compound when M ₂ is a tin atom, and M ₃ Is iodine, and the like.

Specific examples of the ammonium compound include tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB) and tetra-n-butylammonium iodide (TBAI). Ammonium halide (TBAX). Specific examples of the phosphonium compound include tetra-n-butylphosphonium chloride (TBPC) and tetra-n-butylphosphonium chloride.
Tetra n-butyl phosphonium halides (TBP) such as butyl phosphonium bromide (TBPB) and tetra n-butyl phosphonium iodide (TBPI)
X) and tetraphenylphosphonium chloride (T
PPC), tetraphenylphosphonium bromide (T
PPB) and tetraphenylphosphonium halides (TPPX) such as tetraphenylphosphonium iodide (TPPI).

In the present invention, among the above-mentioned quaternary onium salt catalysts, TAC such as TBAC, TBAB and TBAI can be used.
TB such as BAX, TBPC, TBPB and TBPI
The use of ammonium compounds or phosphonium compounds such as PX and TPPX such as TPPC, TPPB and TPPI is preferred. In the present invention, two or more kinds selected from the above quaternary onium salts may be used as a catalyst. The above quaternary onium salt catalyst is used in an amount of 0.1 to 1 mol per mole of the compound represented by the general formula (III).
What is necessary is just to use it in the ratio of 01-0.1 mol. General formula (II
The amount of the compound represented by I) may be twice as much as the calix [4] resorcinarene represented by the general formula (II), but may be less or more than that, The compound represented by the general formula (III) may be used in the range of 1.8 to 3.0 mol per mol of the calix [4] resorcinarene represented by (II).

Calix [4] represented by the general formula (II)
The resorcinol arene is reacted with the compound represented by the general formula (III) under a normal pressure at a temperature of usually 50 ° C to 150 ° C for 1 to 1 hour.
It may be done for 50 hours. The reaction is preferably performed in an atmosphere of an inert gas such as a nitrogen gas, an argon gas, and a helium gas. Stirring is preferred for uniform reaction progress and reaction promotion. The synthesis method of the general formula (I) is as follows.

[0025]

Embedded image (In the above formula, R ₁ , R ₂ and R ₃ are the same as described above.) The oxetane group-containing calix [4] resorcinarene derivative represented by the general formula (I) thus obtained is represented by the following formula Is exemplified.

[0026]

Embedded image

[0027]

Hereinafter, the present invention will be described with reference to examples.
Of course, the present invention is not limited at all by the following examples. (Example 1) (1) Methyl calix [4] resorcinarene (C
Synthesis of RA) In a 50 ml glass autoclave equipped with a stirrer, 1.71 g (15.5 mm) of resorcinol under a nitrogen gas stream.
ol) was dissolved in 20 ml of ethanol, and 1.12 g (15.6 mmol) of acetaldehyde was added.
After dropping 2.5 ml of 12N-HCl aqueous solution on an ice bath, the mixture was stirred for 10 hours while heating to 70 ° C. When the reaction mixture solution was poured into 1 liter of water, a yellow precipitate was deposited. The deposited yellow precipitate was filtered by suction, and heated at 80 ° C. in hot water 2
After washing with liter, the filtrate was finally confirmed to be neutral, and the resulting precipitate was dried by heating to 60 ° C. in a vacuum dryer. The dried product was recrystallized from a mixed solvent of chloroform and ethyl acetate and purified to obtain white granular crystals. At this time, the yield was 72%.

(2) Synthesis of 3-ethyl-3-oxetanylmethyl tosylate (EOMT) 5.81 g (50 mmol) of 3-ethyl-3-hydroxymethyloxetane and 9.53 g (50 mmo)
l) p-Toluenesulfonyl chloride was added to a 100 ml Erlenmeyer flask containing 30 ml of pyridine, and the mixture was reacted at room temperature with stirring for 1 hour. After completion of the reaction, the precipitated pyridine hydrochloride was separated by filtration, the filtered pyridine hydrochloride was washed with ethyl acetate, and the ethyl acetate solution was added to the filtrate. The obtained mixture was transferred to a separating funnel, washed three times with distilled water, and dehydrated by adding magnesium sulfate to the separated organic layer. The magnesium sulfate was collected by filtration, the filtrate was concentrated, and then purified by distillation under reduced pressure. 11.2g
Of EOMT was obtained. The yield is 83%. The physical properties of the obtained EOMT are as follows. bp = 154 ~ 155 ℃ (0.1mmHg) IR (neat, cm ^-1 ) 1597 (ν C = C of aromatic), 1362,11
76 (ν S = O) 1096,980 (ν COC of cyclic ether), 837 (ν SO) ・¹ H-NMR (200MHz, CDCl ₃ , TMS): δ (ppm) 0.84 (t, J = 7.3Hz, 3.0H, CH ₂ CH ₃ ), 1.60-1.84 (q, J = 7.3Hz, 2.
_{0H, CH 2 CH 3) 2.55} (s, 3.0H, Ph- CH 3), 4.26 (s, 2.1H, O- CH 2 -SO 2) 4.32-4.35 (d, J = 6.8Hz, 2.0H, C -CH ₂ -O), 4.38-4.44 (d, J = 6.
_{8Hz, 2.0H, C- CH 2 -O} ) 7.35-7.39 (d, J = 8.1Hz, 2.0H, aromatic H), 7.79-7.83 (d, J
= 8.1Hz, 2.0H, aromaticH)

(3) Oxetane group-containing calix [4]
Synthesis of resorcinarene derivative (1) 0.34 g (2.5 mmol) of CRA, 1.36 g
(5.0 mmol) of EOMT, 0.28 g (5.0
mmol) of KOH, 0.08 g (0.25 mmol)
l) tetra n-butylammonium bromide (TB
AB) containing 1 ml of N-methyl-2-pyrrolidone
The mixture was added to a 0 ml volume of eggplant flask, heated to 70 ° C., and allowed to react for 24 hours while stirring under a nitrogen atmosphere. After the completion of the reaction, the reaction mother liquor was transferred to a separating funnel, chloroform was added, and the mixture was washed three times with distilled water. The separated organic layer was dehydrated by adding magnesium sulfate. After filtering off magnesium sulfate, the residue obtained by concentration was added to ethanol, reprecipitated and purified. The reprecipitation purification operation with ethanol was repeated twice. 0.57 g of a white powder solid was obtained. The yield is 69%. The ¹ H-NMR data of this is as follows. 0.82 (t, J = 7.3 Hz, 12.0 H, CH ₂ C
H ₃ ), 1.02 (t, J = 7.3 Hz, 12.0 H,
CH ₂ CH ₃ ) 1.43 (d, J = 6.8 Hz, 12.0 H, CH CH
₃ ), 1.65 (q, J = 7.3 Hz, 8.0 H, CH
₂ CH ₃ ) 1.92 (q, J = 7.3 Hz, 8.0 H, CH ₂ CH
₃ ), 3.62 (d, J = 5.9 Hz, 8.0H,
^{H a) 3.84 (d, J} = 5.9Hz, 8.0H, H b),
_{4.00-4.34 (m, 12.0H, CH,} CH 2) 4.53 (d, J = 5.9Hz, H a), 4.60-
^{_{4.80 (m, 12.0H, CH 2}} , H b), 6.06
(S, 2.0H, aromatic H) 6.17 (s, 2.0H, aromatic H),
6.54 (s, 2.0H, aromatic H),
7.30 (s, 2.0H, aromatic H)

[0030]

Embedded image

The IR data of a film obtained by dissolving a white powder solid in chloroform and producing a film by a casting method using this chloroform solution is as follows.・ IR (Film, cm ^-1 ) 1457 (ν C = C of aromatic), 1209 (ν
arC-OC of ether) 983 (ν COC of cyclic ether) Further, the elemental analysis value of this white powder solid was C: 72.1.
8% and H: 8.57%, which were in good agreement with the calculated values C: 72.26% and H: 8.49% for the composition formula C ₈₀ H ₁₁₂ O ₁₆ . The ¹ H-NMR spectrum is shown in FIG. 1 and the IR spectrum is shown in FIG. 2 in this specification.

(Example 2) (1) Synthesis of 3-methyl-3-oxetanylmethyl tosylate (MOMT) In the synthesis of (2) EOMT in Example 1, 3-ethyl-3-hydroxymethyloxetane was converted to 3-methyl-3-oxetanylmethyl tosylate (MOMT). Methyl-3-
Example 1 except that hydroxymethyloxetane was replaced
(2). 11.5 g of MOMT were obtained. The yield is 90%.

(2) Calix containing oxetane group [4]
Synthesis of resorcinarene derivative (2) In Example 1, (3), EOMT was replaced with MOMT1.2.
Except having replaced with 8 g (5.0 mmol), it carried out exactly like (3) of Example 1. 0.51 g of a white powder solid was obtained. The yield is 67%. Of this product ¹ H-
The NMR data is as follows.・¹ H-NMR (200 MHz, CDCl ₃ , TMS): δ (ppm) 1.22 (s, 12.0 H, CH ₃ ), 1.45 (d, J = 6.8 Hz, 12.0 H, CH CH ₃ ), 1.52
(s, 12.0H, CH ₃ ) 3.50 (d, J = 5.9Hz, 8.0H, H ^a ), 3.79 (d, J = 5.9Hz, 8.0H, H ^b ) 4.02-4.32 (m, 12.0H, CH , CH ₂ ), 4.50 (d, J = 5.9Hz, H ^a ) 4.60-4.82 (m, 12.0H, CH ₂ , H ^b ), 6.03 (s, 2.0H, aromatic H ^c ) 6.13 (s, 2.0H , aromatic H ^c ), 6.51 (s, 2.0H, aromatic H ^c ),
7.31 (s, 2.0H, aromaticH ^c )

[0034]

Embedded image

The IR data of the film manufactured by the casting method is as follows.・ IR (Film, cm ^-1 ) 1458 (ν C = C of aromatic), 1188 (ν
arC-OC of ether) 975 (ν COC of cyclic ether) The elemental analysis values of the title compound thus obtained are as follows. Obtained: C: 70.96%, H: 8.07% Calculated: C: 71.03%, H: 7.95% (as C ₇₂ H ₉₆ O ₁₆ )

[0036]

By introducing an oxetane group into the calix [4] resorcinarene, heat resistance is maintained and reactivity is imparted, so that its use as various functional materials is further increased.

[Brief description of the drawings]

FIG. 1 shows a ¹ H-NMR spectrum of an oxetane group-containing calix [4] resorcinarene derivative obtained in Example 1.

FIG. 2 shows an IR spectrum of the oxetane group-containing calix [4] resorcinarene derivative obtained in Example 1.

Claims (2)

[Claims] An oxetane group-containing calix [4] resorcinarene derivative represented by the following general formula (I): Embedded image (In the formula, R ₁ represents hydrogen or an alkyl group which may have a C ₁ -C ₁₇ branch, and R ₂ represents hydrogen or an alkyl group which may have a C ₁ -C ₆ branch.) 2. A compound represented by the following general formula (II): (Wherein R ₁ represents hydrogen or an alkyl group which may have a C ₁ -C ₁₇ branch) and calix [4] resorcinarene represented by the following general formula (III): Wherein R ₂ represents hydrogen or an alkyl group which may have a C ₁ -C ₆ branch, and R ₃ represents an alkyl group which may have a C ₁ -C ₄ branch, a phenyl group or p -Representing a tolyl group) in a reaction solvent in the presence of a quaternary onium salt at a temperature of 50 to 150 ° C and a temperature of 1 to 50.
The method for producing an oxetane group-containing calix [4] resorcinarene derivative according to claim 1, wherein the reaction is carried out for a time.