JP2532270B2 - Polyvalent allene compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel polyvalent allene compound and a method for industrially advantageous production thereof.

Among the compounds prior art three carbon atoms have a so-called allene bond attached at two double bonds with each other, phenoxy allene compound represented by the formula _{CH 2 = C = CH-O} -C 6 H 5 Since the publication of homo-radical polymerization of phenoxyallene compound in Polymer Preprints, Japan, 35 (2), 133 (1986) and the like, interest in such phenoxyarene compounds and polymers has been increasing. This is because not only are such phenoxyarene compounds capable of radical polymerization in the same way as vinyl monomers, but they are also radically polymerized into the main chain. A polymer containing a structural unit represented by is obtained, and since it has an ionically polymerizable or radically polymerizable vinyl ether group, an allyl group, or a reactive phenoxy group in the molecule, a new substance based on these is further developed. This is because it is expected to have a wide range of applications in various fields such as coating materials and the way of synthesizing.

The present inventors (In the formula, X is an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
An alkyl group, a halogen or a cyano group of), a propargyl ether derived from a reaction of a substituted phenol represented by (Wherein X is as described above), a large number of substituted phenoxyarene compounds represented by
By its homo-radical polymerization or copolymerization with other α, β ethylenically unsaturated compounds, a reactive polymer having a vinyl ether group, an allyl group, and a substituted phenoxy group was obtained, and a patent application was filed. (Japanese Patent Application No. 62-146370) Problems to be Solved by the Invention The present invention is a further development of these studies, and is a novel allene compound as a raw material of a reactive polymer, especially a new type of polyfunctional allene compound. Is one of the main purposes. It is also an object of the invention to establish an industrially advantageous method for producing such a polyfunctional allene compound.

Means for Solving the Problems According to the present invention, the above-mentioned object is represented by the general formula (Wherein X is a hydrogen atom, a halogen atom, an alkyl group, a cyano group or an alkoxy group; n is an integer of 1 to 4; m is 0 or 1 or 2; and p is an integer of 0 or 1 to 4, provided that m + n +
p = 6), which is achieved by providing a polyvalent allene compound represented by the general formula (1) (Wherein X is a hydrogen atom, a halogen atom, an alkyl group, a cyano group or an alkoxy group; n is an integer of 1 to 4; p is an integer of 0 or 1 to 4, but n + p = 6) 1 mol of a phenol compound And halogenated propargyl n + mmol (m is 0 or 1 or 2; n is 1 to
4, provided that m + n ≧ 2) is reacted and the general formula (In the formula, X, n, p, and m are as described above, provided that m + n
≧ 2, m + n + p = 6) to obtain a phenylpropargyl ether represented by
Further, it can be industrially advantageously produced by a method comprising a step of allenylating the phenylpropargyl ether under basic conditions. Further, among the compounds represented by the general formula [I], for the compound in which m is 1 or 2, (Wherein X is a hydrogen atom, a halogen atom, an alkyl group, a cyano group or an alkoxy group; n is an integer of 1 to 4; p is an integer of 0 or 1 to 4, but n + p = 6). 1 mol of an ether compound was reacted with 1 mol of propargyl halide (m is 1 or 2) with a Friedel-Crafts compound to give a compound of the general formula (Wherein X, n and p are each as described above, m is 1 or 2, provided that m + n + p = 6), and a step of obtaining the polyvalent propargyl compound under basic condition with allenyl It can also be produced industrially advantageously by a method comprising a step of converting into a compound.

We have the formula (Wherein X, n, and p are as described above), within a range of equimolar amounts of a propargyl halide such as propargyl bromide to a phenolic hydroxyl group, relative to the monohydric or polyhydric phenol. When reacted, propargyl phenyl ether is obtained, but when used in a larger excess, not only etherification of the phenolic hydroxyl group but also formula [III] in which the propargyl group is substituted on the benzene ring is shown. It has been found that a polyvalent propargyl compound can be obtained in a high yield, and that allenylation can be easily carried out by the isomerization reaction thereof to obtain an allene compound represented by the general formula [I] of the present invention. The invention was completed.

When a large excess of halogenated propargyl is allowed to act on phenol, some of the phenolic hydroxyl groups become propargyl ether depending on the reaction conditions, and a small amount of other compounds, etc., which remain as hydroxyl groups together with the raw materials. Although it may remain, the target compound can be isolated by using, for example, thin layer chromatography.

Following the above, phenylpropargyl ether was added to t-
The polyvalent allene compound of the present invention can be industrially advantageously produced by isomerizing basic alcohol such as butanol potassium alcoholate.

The compound of the present invention in which the polyvalent allene compound is 1 or 2 in m is also a known phenoxypropargyl ether obtained by reacting a substituted or unsubstituted phenol with a predetermined amount of propargyl bromide. (Wherein X, n and p are as described above), a propargyl halide is reacted by Friedel-Crafts reaction (In the formula, X is a hydrogen atom, a halogen group, an alkyl group, a cyano group or an alkoxy group; n is an integer of 1 to 4; p is an integer of 0 or 1 to 4; m is 1 or 2, provided that m + n + p =
A polyvalent propargyl compound represented by 6) is obtained, and it can be industrially advantageously produced by a method of allenylating the compound.

The Friedel-Crafts reaction in this case is carried out according to a conventional method by reacting the starting compound in an inert solvent with a Lewis acid catalyst such as anhydrous aluminum chloride,
Depending on the amount of propargyl halide, 1-2 molecules of propargyl groups are introduced into the phenyl nucleus.

The polyhydric propargyl compound is then subjected to an isomerization reaction under basic conditions using, for example, potassium alcoholate of t-butyl alcohol, It is led to the target polyvalent allene compound.

Each step of the method of the present invention can proceed in high yield, and the novel polyvalent allene compound represented by the general formula [I] can be industrially produced advantageously.

The polyvalent allene compound according to the present invention can give a reactive polymer useful in the paint field or the like by polymerization alone or with another α, β-ethylenically unsaturated compound, and thus is extremely useful as a polymer raw material. Is.

 The present invention will be described below with reference to examples.

Example 1 A flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser was charged with 1,4-dihydroxybenzene.
3.469 g, ion-exchanged water 44.037 g, NaOH 11.070 g, tetrabutylammonium bromide 0.134 g were added and dissolved, and then propargyl bromide 31.288 g was added dropwise over 15 minutes, and the mixture was reacted at 80 ° C. for 6 hours.

After the reaction was completed, the content was treated with ether / DIW and 1N-NaOH aqueous solution, and the ether layer was separated. Thereafter, magnesium sulfate was added, and the mixture was allowed to stand overnight to be dehydrated. After filtering magnesium sulfate, the ether was distilled off with an evaporator,
An oily substance was obtained. Then, it was isolated and purified by column chromatography (silica gel mesh 200) using ethyl acetate / hexane as a developing solvent to obtain 1,4-dipropargyloxybenzene. Yield: 79.6 (%) Then, using the same reactor, t-BuOK 2.984
After weighing 16.906 g of g and t-BuOH and completely dissolving them,
1,4-Dipropargyloxybenzene 10.00 g was added to t-BuOH
What was melt | dissolved in 23.333g was dripped over 15 minutes. Then, the reaction was carried out at a temperature of 60 ° C. for 30 minutes, and then ion-exchanged water was added to stop the reaction.

The t-BuOH layer / water layer was separated, and the water layer was further subjected to ether extraction, and both the t-BuOH layer and the ether layer were distilled off with an evaporator to obtain a brown oily substance.

Using ethyl acetate / hexane as a developing solvent,
Column chromatography (silica gel mesh 20
0) isolated and purified by white crystals (melting point: 34.2-36.7 ℃)
To obtain 1.4-dialenenyloxybenzene. The structure was confirmed by FT-NMR (H) IR. Yield: 62.3 (%) Example 2 A flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser was charged with 1,3,5-trihydroxybenzene.
15.644 g, ion-exchanged water 34.734 g, NaOH 12.446 g, and tetrabutylammonium bromide 0.158 g were added and dissolved, and then propargyl bromide 37.018 g was added dropwise over 15 minutes, and the mixture was reacted at 80 ° C. for 10 hours.

After the reaction was completed, the content was treated with ether / DIW and 1N-NaOH aqueous solution, and the ether layer was separated. Thereafter, magnesium sulfate was added, and the mixture was allowed to stand overnight to be dehydrated. After filtering magnesium sulfate, the ether was distilled off with an evaporator,
An oily substance was obtained. Then, it was isolated and purified by column chromatography (silica gel mesh 200) using ethyl acetate / hexane as a developing solvent to obtain 1,3,5-tripropargyloxybenzene. Yield: 56.8 (%) Then, using the same reactor, t-BuOK 3.015
g, t-BuOH 17.070 g was weighed and completely dissolved,
3,5-Tripropargyloxybenzene 10.00 g was added to t-Bu
What was dissolved in 23.333 g of OH was added dropwise over 15 minutes. Then, the reaction was carried out at a temperature of 50 ° C. for 60 minutes, ion-exchanged water was added to stop the reaction.

The t-BuOH layer / water layer was separated, and the water layer was further extracted with ether, and both the t-BuOH layer and the ether layer were distilled off with an evaporator to obtain a brown oily substance.

Using ethyl acetate / hexane as a developing solvent,
Column chromatography (silica gel mesh 20
0) was isolated and purified to obtain colorless oily 1,3,5-triarenyloxybenzene.

The structure was confirmed by FT-NMR (H) and IR. yield:
52.3 (%) Example 3 To a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser, 10.879 g of phenol, 20.808 g of ion-exchanged water, and 5.340 g of NaOH were added, and then 14,784 g of propargyl bromide was added over 15 minutes. Drop at 40 ° C for 15
Allowed to react for hours. After purification, AlCl ₃ and 14.784 g of propargyl bromide were further added, and the reaction was carried out for 10 hours. After the reaction was completed, the contents were separated by ether / DIW. Thereafter, magnesium sulfate was added, and the mixture was allowed to stand overnight to be dehydrated. After filtering magnesium sulfate, the ether was distilled off with an evaporator to obtain an oily substance. Then, it was isolated and purified by column chromatography (silica gel mesh 200) to obtain 1-propargyloxy-4-propargylbenzene. Yield: 26.7 (%) ν (-CH 2 -C≡CH) 1420cm-1 followed using a similar reactor t-BuOK 1.492g,
Weigh out 8.453 g of t-BuOH, dissolve it completely, and then
A solution of 5.0 g of propargyloxy-4-propargylbenzene dissolved in 11.667 g of t-BuOH was added dropwise over 15 minutes. Then, the reaction was carried out at a temperature of 50 ° C. for 60 minutes, ion-exchanged water was added to stop the reaction.

The t-BuOH layer / water layer was separated, and the water layer was further extracted with ether, and both the t-BuOH layer and the ether layer were distilled off with an evaporator to obtain a brown oily substance.

Then, it was isolated and purified by color chromatography (silica gel mesh 200) to obtain colorless oily 1-allenyloxy-4-arenylbenzene.

The structure was confirmed by FT-NMR (H) and IR. yield:
52.3 (%) Examples 4 to 7 In the same manner as in Example 1, except that the raw materials were changed, the following compounds were obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 255/54 C07C 255/54 // C08F 36/02 MPM C08F 36/02 MPM (72) Inventor Kei Aoki 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Keizo Ishii 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd.

Claims (3)

(57) [Claims] 1. A general formula (In the formula, X is a hydrogen atom, a halogen atom, an alkyl group, a cyano group or an alkoxy group; n is an integer of 1 to 4; m is 0 or 1 or 2; p is an integer of 0 or 1 to 4, provided that m +
a polyvalent allene compound represented by n ≧ 2, m + n + p = 6). 2. General formula (Wherein X is a hydrogen atom, a halogen atom, an alkyl group, a cyano group or an alkoxy group; n is an integer of 1 to 4; p is an integer of 0 or 1 to 4; provided that n + p = 6). Moles and halogenated propargyl n + m moles (m is 0 or 1 or 2; n is 1 to 4,
However, by reacting m + n ≧ 2), the general formula (Where X, n, p, and m are as described above, provided that m +
n ≧ 2, m + n + p = 6) to obtain phenylpropargyl ether
The process for producing a polyvalent allene compound according to claim 1, which comprises a step of allenylating the phenylpropargyl ether under basic conditions. 3. General formula (Wherein X is a hydrogen atom, a halogen atom, an alkyl group, a cyano group or an alkoxy group; n is an integer of 1 to 4; p is 0 or an integer of 1 to 4, provided that n + p = 6). 1 mol of the compound is reacted with 1 mol of propargyl halide (where m is 1 or 2) by Friedel-Crafts reaction. (Wherein X, n and p are each as described above, m is 1 or 2, provided that m + n + p = 6), and a step of obtaining the polyvalent propargyl compound under basic condition with allenyl. The method for producing a polyvalent allene compound according to claim 1, wherein m is 1 or 2.