JPS5984845A - 2-biphenyl acrylate and its preparation - Google Patents

Abstract

NEW MATERIAL:A 2-biphenyl (meth)acrylate shown by the formula (R is H, or methyl). USE:Useful as an antiseptic, antimicrobial agent, antifungal agent, repellent for noxious insects, etc. Prepared as a polymerizable monomer, it has improved dispersibility and compatibility, keeping durability. Advantageous with respect to pollution and environmental contamination in terms of economy and reduction in energy. PROCESS:2-Biphenylol is reacted with an acylating agent (e.g., acryloyl chloride, methacryloyl chloride, etc.) shown by the formula CH2=CR-COX(X is halogen, or acyloxy to form acid anhydride) in the presence of a nitrogen-containing organic base (e.g., tertiary amine such as triethylamine, pyridine, etc.) in an organic solvent at -29-80 deg.C, preferably at 0-40 deg.C for 30min several hours, to give a compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel polymerizable monomer, 2-biphenyl (
This invention relates to meth)acrylate and its manufacturing method.

Conventionally, 2-biphenylol, also called ortho-phenylphenol, has been used in many ways as a preservative, an antibacterial agent, an antifungal agent, an insect repellent, and the like. However, since it has extremely high water solubility and sublimability, and has a fast outflow rate, it is necessary to add and mix an excess amount of 2-biphenylol in order to maintain sustainability over a long period of time. The use of excessive needles not only reduces product performance but is also uneconomical.
Ultimately, it causes drug damage and leads to environmental destruction.

As a method to solve this drawback, it is possible to convert 2-biphenylol into a polymerizable monomer by acylation. By polymerizing this monomer, it is possible to obtain a polymer with excellent properties that has long-lasting properties and sustained release properties at the minimum required amount without using excess 2-biphenylol. . In addition, by making these 9 monomers pendant in a polymer, it is possible to improve the dispersibility and compatibility in the product and prevent deterioration in product performance.In addition, it is possible to prevent deterioration in product performance, as well as to reduce pollution and environmental contamination. You can also expect from

Therefore, as a result of intensive research on 2-biphenyl (meth)acrylate, a new compound with the above-mentioned properties, and its production method, the present inventor found that using a nitrogen-containing organic base as the base yields high yields under mild reaction conditions. It was discovered that a stable target product could be obtained, and the present invention was completed.

That is, the first invention of the present invention provides 2-biphenyl (meth)acrylate represented by the following general formula (in the above formula, R represents hydrogen or a methyl group); is the general formula % of Niggi in the presence of a nitrogen-containing organic base in 2-biphenylol in an organic solvent. (Indicates an acyloxy group.)
It is characterized by reacting with an acylating agent shown in

The present invention provides a method for producing 2-biphenyl (meth)acrylate represented by the general formula (in the above formula, R represents hydrogen or a methyl group).

The 2-biphenyl (meth)acrylate company of the present invention confirmed the existence of a diester bond terminal unsaturated double bond and benzene atom by infrared spectral analysis (hereinafter referred to as IR), and conducted nuclear magnetic resonance spectroscopy (hereinafter referred to as NMR). It is identified by determining the position and state of the cyproton.

The 2-biphenyl (meth)acrylate of the present invention is 2-
Produced by acylating biphenylol.

The organic solvent used in the present invention is not particularly limited, but
For example, aliphatic hydrocarbons such as heptane, hexane, and petroleum ether, aliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, and linear and cyclic hydrocarbons such as diethyl ether, dioxane, and tetrahydrofuran. One or a mixture of two or more of ethers, glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and ketones such as acetone and methyl ethyl ketone are used. Further, highly polar organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and hexamethylphosphoamide are also used alone or in combination with other organic solvents as described above.

As the nitrogen-containing organic base used in the present invention, tertiary amines are suitable. Specifically, triethylamine, tributylamine, N,N-dimethylbenzylamine,
Examples include N-methylpiperidine, N,N,N',N'-tetramethyl-1,2-diaminoethane, pyridine, 1,8-diazabicyclo(s,4.o)-7-undecene, and the like.

Acylating agent i1 for acylating 2-biphenylol in the present invention: the above general formula, CIT2 = CR-C
It is an acyloxy group that forms an acid anhydride represented by the general formula OX, CH2=CR-C'00- (where R is hydrogen or a methyl group).

Preferred acylating agents in the present invention include methacroyl chloride, acryloyl chloride, methacroyl bromide, acryloyl bromide, methacrylic anhydride, and acrylic anhydride.

In the present invention, the nitrogen-containing organic base is used in an equimolar amount relative to the acylating agent, but it may be used in an equimolar or more amount. The acylating agent is preferably used in an equimolar amount relative to 2-biphenylol, but may be used in an equimolar or more or an equimolar or less amount.

The production method of the present invention is carried out by dissolving or dispersing and suspending 2-biphenylol in a solution of a nitrogen-containing organic base, and dropping a solution of an acylating agent into this solution or dispersed suspension while stirring. is normal. The reaction temperature is
2-biphenyl (meth), which is not particularly limited but is frequently produced.
Undesirable side reactions such as polymerization of acrylate may occur, which is not very preferable. The time required for the reaction is
The reaction time is usually 30 minutes to several tens of hours, depending on the reaction temperature #1, the acylating agent used, and the type of base. After the reaction is complete, insoluble materials including by-products are separated and the F solution is purified.Although the solvent is of high purity, if further purification is necessary, it can be purified by distillation, column chromatography, or other appropriate means. can.

According to the method of the present invention, 2-biphenyl (meth)acrylate is stably obtained in high yield by reacting 2-biphenylol with an acylating agent under mild reaction conditions using a nitrogen-containing organic base. be able to.

The 2-biphenyl (meth)acrylate of the present invention is a polymerizable monomer, and can be made into a bactericidal, antifungal, and antiseptic resin by polymerization or monopolymerization.

The 2-biphenyl (meth)acrylate of the present invention itself is hardly toxic, but when it is decomposed by water and released from the resin, it becomes 2-biphenylol, which exhibits strong bactericidal properties. .

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 34.0 2-biphenylol in 250 ml of benzene
y (0,20 mol) and triethylamine 2o, 2r
(o, zo mol) was added thereto, and a solution of 19.9 y (0.22 mol') of acryloyl chloride in 50 ml of benzene was gradually added dropwise to this with stirring.
Allowed time to react. After the reaction is complete, remove the insoluble matter and pour the furnace liquid into 1
It was washed twice with 200ml of 0% aqueous sodium hydrogen carbonate solution and then three times with 200ml of water. After drying the benzene layer with anhydrous sodium sulfate, the benzene was distilled off under reduced pressure to give a solution of 44.0
A crude product of 2 was obtained.

The crude product was purified by silica gel column chromatography to obtain 41.59 colorless liquid. The yield was 93 times.

This colorless liquid was confirmed to be 2-biphenylacrylate based on the results of iR, NAqR and elemental analysis17
is.

IR (liquid film v): 3020, 3010, 173
0°1625.1620,1500,1470,139
0゜1290.1140,970,8'90 (m-'
) Note: 1730tM-' is the absorption of cmc-c-o-, 1625゜1 1620 Crn-' is the absorption of CH2=CI(-, 1
500 cm-'' represents the absorption of the benzene ring.

NMR(CD C6s+δ)(ppm) 5.7
8-6. oo (m, LH) Shows the 9 protons at the top of benzene) Note: Shows the protons at the knee.

↑ Example 2 Diethyl ether 50 meK 2-biphenylol-0,Of (0,0588 mol) and pyridine 5.
6? (0,0709 mol) and to this was added methacryloyl chloride while stirring.7. , if (o, 0705
mole) of 3t1++d! A diethyl ether solution was gradually added dropwise, and after the addition was completed, the reaction was carried out at reflux temperature for 7 hours. The crude product 13.3 f was obtained in the same manner as in Example 1.

Purification was carried out in the same manner as in Example 1 to obtain a colorless liquid. Yield is 90
%Met.

This colorless liquid was confirmed to be 2-biphenyl methacrylate from the results of IR, NMR and elemental analysis.

rR (liquid film ν): 3020, 3010.17 a
o.

1 (i 25,1620,1500,147.0,1
390°129 n, 1140,970,890 (m-
') Note: Same as the example work NMR (CDC15, δ) (ppm) x, 9s
(d, aH) (9 protons on benzene product) Sou: Shima fpl ly J) C Example 3 Dioxane 150 mg K2-biphenylol a, s
1y (0,05 mol) and 1.8-) azapisic o (5,4,0) -7-undesy7.6Of (0
, os equivalent moles were added thereto, and a Some dioxane solution of 7.7 of methacrylic anhydride (o, os equimole) was gradually added dropwise to this while stirring. After the dropwise addition was completed, the reaction was allowed to proceed for 10 hours in the width of the room.Example Process in the same way as 1 and add 2 to bifuenimelme
1016 h-lylate crude products were obtained. The yield after purification was 85%.

The results of I n , NMR and elemental analysis were substantially the same as in Example 2.

Patent applicant: NOF Corporation

Claims (1)

[Scope of Claims] 1. 2-piphenyl (meth)acrylate represented by the following general formula (in the above formula, R represents hydrogen or a methyl group). 2 In the presence of a nitrogen-containing organic base, 2-biphenylol is added to 2-biphenylol in an organic solvent to form the following general formula (% formula %) (In the above formula, R represents hydrogen or a methyl group, and X represents a halogen or an acyloxy group forming an acid anhydride. (indicates the group)
characterized by reacting an acylating agent represented by
A method for producing 2-piphenyl (meth)acrylate represented by the following general formula % (in the above formula, R represents hydrogen or a methyl group). 3. The method for producing 2-biphenyl (meth)acrylate according to claim 2, wherein the nitrogen-containing organic base is a tertiary amine.