JPH1180264A - Allenyloxymethylnaphthalene, its preparation and polymer obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer being useful as e.g. a carrier for medicines and agricultural chemicals and made from a monomer being allenyloxymethylnaphthalene obtained by isomerizing propargyloxymethylnaphthalene. SOLUTION: The allenyloxynaphthalene represented by formula I (wherein R<1> and R<2> are each H, an alkyl, an alkoxy or an aryl; p is 1-4; and q is 1-3) is obtained by isomerizing a propargyloxymethylnaphthalene of formula IV obtained by reacting a bromonaphthalene of formula II with propargyl alcohol of formula III. Next, the propargyloxymethylnaphthalene of formula IV is polymerized to obtain an allenyloxynaphthalene polymer represented by formula V (wherein R<1> , R<2> , p and q are as defined in formula I; and X and Y are each 0-100). The isomerization reaction can be carried out in the presence of a basic catalyst such as sodium t-butoxide or potassium t-butoxide. It is desirable that the polymerization reaction is carried out in the presence of a coordination catalyst such as a π-allyl nickel catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to allenyloxymethylnaphthalene, a polymer thereof, and a method for producing the same.

[0002]

2. Description of the Related Art Acetylene compounds (propargyl derivatives)
Allenes, which are isomers of, are obtained by isomerizing a propargyl precursor with a basic catalyst system, adding dibromocarbene to a precursor having a double bond and treating this with a base, and propargyl ether species. Synthesized by a method of reacting organomagnesium in the presence of a copper catalyst or the like, and as substituted allenes, phenylarene (Literature;
a, N .; Ito, T .; Endo, Chem. Let
t. , 1955, 1988), alkoxyallenes (literature; T. Yokozawa, M. Tanaka, TE).
ndo, Chem. Lett. , 1831, 1987,
J. Mizuya, T .; Yokozawa, T .; End
o, Part A: Polym. Chem. , 26,31
19, 1988), allenylpyrrolidone (literature; J.L.
eland, J. et al. Boucher, K .; Anders
on, J.M. Polym. Sci. Polym. Ch
em. Ed. , 15, 2785, 1977), allenyl oxazolidone (literature; Y. Tachibana, T .;
Tanaka, T .; Endo, Polym. Prep
r. Jpn. , 41, 219, 1992), and their polymerization reactions have been studied. However, allyloxymethylnaphthalene, which is an allene derivative having a naphthalene ring, and its polymer are unknown compounds. .

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel and useful allenyloxymethylnaphthalene compound and a novel polymer using the same as a monomer.

[0004]

Means for Solving the Problems A first aspect of the present invention is the following general formula (1):

Embedded image (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 Allyloxymethylnaphthalene).

A second aspect of the present invention is the following general formula (2)

Embedded image (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 At least one bromomethylnaphthalene represented by the following formula (3):

Embedded image The following general formula (4) obtained by reacting with propargyl alcohol represented by

Embedded image (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 Wherein propargyloxymethylnaphthalene represented by the following general formula (1) is isomerized:

Embedded image (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 Which is an integer).

A third aspect of the present invention is the following general formula (5):

Embedded image (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 X is an integer of 0 to 100, Y is an integer of 0 to 100, and X and Y are not both 0.) Allenyloxymethyl It relates to a naphthalene polymer.

A fourth aspect of the present invention is the following general formula (1):

Embedded image (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 Wherein at least one kind of allenyloxymethylnaphthalene represented by the following general formula (5) is polymerized:

Embedded image (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 X is an integer of 0 to 100, Y is an integer of 0 to 100, and X and Y are not both 0.) Allenyloxymethyl The present invention relates to a method for producing a naphthalene polymer.

[0008] The isomerization of propargyloxymethylnaphthalene can be carried out in the presence of a basic catalyst. The basic catalyst is not particularly limited, but may be an alcoholate of an alkali metal, for example, sodium-t.
-Butoxide, potassium-t-butoxide and the like.

The polymerization reaction of the present invention is preferably carried out in the presence of a basic catalyst or a coordination catalyst such as a π-allylic nickel catalyst.

Examples of the alkyl group represented by R ¹ and R ² include methyl, ethyl, propyl, butyl, sec-butyl and t-butyl. Examples of the alkoxy group include methoxy, ethoxy, propoxy and butoxy. Examples of the aryl group include phenyl, alkyl-substituted phenyl, and alkoxy-substituted phenyl. The alkyl and alkoxy substituents may be the above-described alkyl and alkoxy groups.

[0011]

EXAMPLES The present invention will be described below with reference to production examples and examples, but the present invention is not limited thereto.

Production Example 1 (Synthesis of 2-bromomethylnaphthalene)

Embedded image Under a nitrogen atmosphere, carbon tetrachloride (50 ml) and 2-methylnaphthalene (18.16 g,
127.7 mmol), N-bromosuccinimide (N
BS) (25 g, 140.5 mmol) and benzoyl peroxide (0.1 g, 0.4 mmol) were added, stirred with a magnetic stirrer, and reacted at 80 ° C. for 6 hours.
After the reaction, the suspended matter was filtered, carbon tetrachloride as a reaction solvent was distilled off under reduced pressure, and the residue was recrystallized with hexane to obtain 2- (bromomethyl) naphthalene as an intermediate. Yield 88.
2% (mp 51-54 ° C).

Example 1 Part 1: Synthesis of 2-propargyloxymethylnaphthalene

Embedded image Under a nitrogen atmosphere, tetrahydrofuran (THF) (20 ml) and propargyl alcohol (1.90 g, 33.9 mmol) were placed in a reaction vessel equipped with a condenser and a dropping funnel.
Was added, and n-butyllithium hexane solution (1.6 N, 21.2 ml, 33.9 mmol) was added thereto under ice cooling, and the 2- (bromomethyl) naphthalene (5 g, 22) obtained in Production Example 1 was obtained from the dropping funnel. .6 mmol) T
The HF solution was added dropwise and refluxed for 3 hours. After the reaction, the suspension was filtered, and THF as a reaction solvent was distilled off under reduced pressure.
2-Propargyloxymethylnaphthalene as an intermediate was isolated by column chromatography (filler: SiO ₂ , developing solvent: n-hexane: diethyl ether = 10: 1). Yield 47.4%.

In the resulting 2-propargyloxymethylnaphthalene, underlined H or C
Are as follows. ¹ H-NMR (90 MHz, CDCl ₃ , δ in pp
m) 2.44 (t, J = 2.4 Hz, 1 H, H C ≡);
12 (d, J = 2.2,2H, -C H 2 -C≡), 4.
_{66 (s, 2H, C 10} H 7 C H 2 -), 7.33~7.7
_{9 (m, 7H, C 10} H 7 -). ¹³ C-NMR (90 MHz, CDCl ₃ , δ in pp
_{m) 56.89 (-O C H 2} C≡), 71.34 (C 10 H 7 C
_{H 2 -), 74.64 (-C≡} C H), 79.60
_{(-CH 2 C ≡CH), 125.77} (C 10 H 7 -),
_{125.92 (C 10 H 7 -)} , 126.42 (C 10 H
_{7 -), 126.68 (C 10} H 7 -), 127.51
( C ₁₀ H ₇ −), 127.70 ( C ₁₀ H ₇ −), 12
_{8.03 (C 10 H 7 -)} , 132.87 (C 10 H
_{7 -), 133.06 (C 10} H 7 -), 134.62
(C ₁₀ H ₇ -).

Part 2: Synthesis of 2-Allenyloxymethylnaphthalene

Embedded image It was synthesized by isomerizing 2-propargyloxymethylnaphthalene. Under a nitrogen atmosphere, add tetrahydrofuran (TH
F) (20 ml), potassium-t-butoxide (0.8
7 g, 7.7 mmol, 30 mol%), and 2-propargyloxymethylnaphthalene (5.05 g, 25.7 mmol) obtained from the dropping funnel by the above method.
Was added dropwise and refluxed for 3 hours. After the reaction, the suspended matter was filtered, and THF as a reaction solvent was distilled off under reduced pressure. Then, 2-allenium was subjected to column chromatography (filler: SiO ₂ , developing solvent: n-hexane: diethyl ether = 10: 1). Roxymethylnaphthalene was isolated. Yield 65.0%.

[0016] 2-Allenyloxymethylnaphthalene
NMR analysis of underlined H or C
Are as follows.¹ H-NMR (90 MHz, CDCl_Three, Δ in pp
m) 4.77 (s, 2H, C_TenH₇CH ₂ −), 5.475
(D, 2H, J = 5.9 Hz, 2H, = C = CH ₂ ),
6.87 (t, 1H, J = 5.7 Hz, -CH= C = C
H_Two), 7.40-7.87 (m, 7H, C_Ten H ₇ −).¹³ C-NMR (90 MHz, CDCl_Three, Δ in pp
m) 70.7 (C_TenH₇ CH_Two−), 91.2 (= C =C
H_Two), 121.6 (-CH = C = CH_Two), 125.6.
(C ₁₀ H₇−), 126.0 (C ₁₀ H₇−), 12
6.1 (C ₁₀ H₇−), 126.7 (C ₁₀ H₇−),
127.7 (C ₁₀ H₇−), 127.9 (C ₁₀ H
₇−), 128.1 (C ₁₀ H₇−), 133.0 (C
_Ten H₇−), 133.2 (C ₁₀ H₇−), 134.8
(C ₁₀ H₇−), 201.3 (−CH =C= CH_Two)

Example 2 (Synthesis of polymer by coordination polymerization of 2-allenyloxymethylnaphthalene)

Embedded image Under a nitrogen atmosphere, a toluene solution of π-allyltrifluoroacetic acid (1.0 M, 24 ml) and a toluene solution of Ni (cod) ₂ (0.085 M, 0.24 ml) were placed in a reaction vessel equipped with a condenser and a dropping funnel. After stirring for several minutes, a toluene solution of triphenylphosphine (PPh ₃ ) (1.0 M, 24 ml) was added, and 2-allenyloxymethylnaphthalene (0.196 g,
1 mmol) was added dropwise, and a polymerization reaction was performed at room temperature for 24 hours. The reaction solution was reprecipitated in diethyl ether to obtain a polymer. Yield: 96.1%. Molecular weight: 8,200. x: y = 3:
7

In the above polymer, an underline is
Chemical shift values of the attached H or C NMR analysis are as follows:
It is as described.¹ H-NMR (90 MHz, CDCl_Three, Δ in pp
m) 2.64 (-CH ₂ −), 4.00 to 4.52 (−CH
−, C_TenH₇CH ₂ −), 4.7 to 5.3 (= CH ₂ ),
5.95 (-OCH=), 6.9-7.8 (C_Ten H
₇ −).¹³ C-NMR (90 MHz, CDCl_Three, Δ in pp
m) 28.7 (-CH_Two−), 69.4 (−CH-), 7
2.9 (C_TenH₇ CH_Two−), 114.3 (=C
H_Two), 125.3 (C ₁₀ H₇−), 125.7
(C ₁₀ H₇−), 127.5 (C ₁₀ H₇−), 12
7.8 (C ₁₀ H₇−), 128.2 (C ₁₀ H₇−),
 129.0 (C ₁₀ H₇−), 132.7 (C ₁₀ H
₇−), 133.0 (C ₁₀ H₇−), 135.4
(C ₁₀ H₇−), 137.0 (C ₁₀ H₇−), 14
2.4 [-C(= C)-], 145.0 (=CH-O
−).

The obtained polymer is soluble in organic solvents such as chloroform, methylene chloride and THF. FIG. 1 shows the structure and ¹ H-NMR spectrum of the polymer. From the ¹ H-NMR spectrum shown in FIG. 1, peaks a derived from the double bond of the 1,2-polymerization unit and b derived from the double bond of the 2,3-polymerization unit were 5.9 and 5 respectively. It was observed at 0.0 ppm, and from the integration ratio, the ratio of 1,2 polymerization to 2,3 polymerization units of the obtained polymer was about 3 to 7. The result of preferential formation of the 2,3-polymerization unit in the present polymerization system is in good agreement with the report of coordination polymerization of alkoxyallenes. It is considered that a 2,3-polymerized unit in which a double bond farther from the substituent is polymerized than the polymerized unit is preferentially generated. In addition, regarding the double bond present in the polymer, the result of calculating the residual ratio of the double bond by comparing the integral ratio between the olefin peak and the other peaks shows that the double bond remains almost quantitatively in the polymer. Was confirmed. In the synthesis of a polymer by coordination polymerization of 2-allenyloxymethylnaphthalene, an example in which the charge ratio of the monomer to the initiator was changed is shown below.

Example 3 The amount of the monomer added was 20 relative to the initiator π-allyl nickel trifluoroacetate catalyst (2 mol%).
Then, 1.2 equivalents of triphenylphosphine as a ligand were added to nickel, and a polymerization reaction was carried out in toluene under a nitrogen atmosphere at room temperature for 24 hours. The reaction solution was reprecipitated in diethyl ether to obtain a polymer. Yield: 8
2.5%. Molecular weight: 3,800.

Example 4 The amount of the monomer added was 50 relative to the initiator π-allyl nickel trifluoroacetate catalyst (2 mol%).
Then, 1.2 equivalents of triphenylphosphine as a ligand were added to nickel, and a polymerization reaction was carried out in toluene under a nitrogen atmosphere at room temperature for 24 hours. The reaction solution was reprecipitated in diethyl ether to obtain a polymer. Yield: 9
6.2%. Molecular weight: 8,200.

Example 5 The amount of the monomer added was 10 relative to the initiator π-allyl nickel trifluoroacetate catalyst (2 mol%).
The equivalent was 0 equivalent, triphenylphosphine as a ligand was added in an amount of 1.2 equivalents to nickel, and a polymerization reaction was performed in toluene under a nitrogen atmosphere at room temperature for 24 hours. The reaction solution was reprecipitated in diethyl ether to obtain a polymer. yield:
91.3%. Molecular weight: 17,900.

With respect to the polymers obtained in Examples 3 to 5, in the coordination polymerization of 2-allenyloxymethylnaphthalene with π-allylnickel trifluoroacetate catalyst, the charge ratio of the monomer to the initiator, and the molecular weight and molecular weight of the resulting polymer The distribution is shown in the table below.

[0024]

[Table 1] Charge ratio of monomer to initiator of coordination polymerization using π-allyl nickel trifluoroacetate catalyst, molecular weight (Mn) and molecular weight distribution (Mw / Mn) of formed polymer ━━━━━━━━━━━━━━━━━━━━━━━━━━━ [Monomer] / [Initiator] Yield (%) Mn Mw / Mn ━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 3 20 82.5 3,800 1.04 Example 4 50 96.2 8 , 200 1.06 Example 5 100 91.3 17,900 1.02 { Π Charge ratio of monomer to initiator for coordination polymerization with π-allyl nickel trifluoroacetate catalyst in Table 1 and polymer produced Molecular weight (Mn) and molecular weight distribution (Mw
/ Mn) is shown in FIG.

As shown in FIG. 2, the molecular weight of the polymer obtained by the coordination polymerization increases linearly with the charge ratio of the monomer to the initiator, and the polymer having the molecular weight corresponding to the charge ratio of monodispersion is increased. Obtained. In addition, even when the charge ratio of the monomer increases, the molecular weight distribution of the polymer is constant, and it can be estimated that the coordination polymerization of 2-allenyloxymethylnaphthalene with the π-allyl nickel catalyst is a reaction by a living mechanism.

[0026]

【effect】

(1) A novel compound, allenyloxymethylnaphthalene, and a method for producing the same were provided. (2) A novel allenyloxymethylnaphthalene polymer and a method for producing the same can be provided. (3) According to the present invention, a method for effectively utilizing methylnaphthalenes in a petroleum fraction can be enriched. (4) The polymer is a waxy or solid polymer, which has a large number of double bonds, so that various compounds can be added to it, so that pharmaceuticals, agricultural chemicals, etc. Can also serve as a carrier.

[Brief description of the drawings]

FIG. 1 shows the structure of the polymer obtained in Example 2 of the present invention and the corresponding ¹ H-NMR spectrum.

FIG. 2 shows the relationship between the charge ratio of monomers and the molecular weight and molecular weight distribution of the produced polymer.

Claims (4)

[Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 Allyloxymethylnaphthalene represented by the following formula: 2. The following general formula (2): (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 At least one bromomethylnaphthalene represented by the following formula (3): The following general formula (4) obtained by reacting with propargyl alcohol represented by the following formula: (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 Which is an integer) isomerizing propargyloxymethylnaphthalene represented by the following general formula (1): (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 A process for producing allenyloxymethylnaphthalene represented by the formula: 3. The following general formula (5): (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 X is an integer of 0 to 100, Y is an integer of 0 to 100, and X and Y are not both 0.) Allenyloxymethyl Naphthalene polymer. 4. The following general formula (1): (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 Wherein at least one kind of allenyloxymethylnaphthalene represented by the following general formula (5) is polymerized: (Wherein, R ¹ and R ² are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group and an aryl group, p is an integer of 1 to 4, and q is 1 to 3 X is an integer of 0 to 100, Y is an integer of 0 to 100, and X and Y are not both 0.) Allenyloxymethyl Manufacturing method of naphthalene polymer.