JPH01199973A - Production of ester - Google Patents

Abstract

PURPOSE:To subject a bicyclo compound to ring opening and to simultaneously obtain an ester to which an acid halide is added, by reacting a bicyclo compound containing 2,6,7-trioxabicyclo[2,2,2]octane group with the acid halide. CONSTITUTION:A bicyclo compound such as a compound shown by formula I (R1 is H, alkyl, aralkyl, aryl, etc.; R2 is H, alkyl, aryl, alkaryl, etc.) or formula II (R3A is aryl; R4 is alkyl, aralkyl, aryl, etc.; m is >=2) containing one or more 2,6,7-trioxabicyclo[2,2,2]octane groups is reacted with an acid halide compound containing one or more acid halide groups (with the proviso that a case where each compound containing two or more groups is omitted) to give an ester. This reaction can be carried out in any form depending upon use of the ester and for example, when the ester is used as an adhesive, the compound and the acid halide are applied to a face to be bonded and the reaction is effected in a contact state of materials to be bonded and when used as a molding material, the reaction is performed in a state of being cast in a mold.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 2,6,7-1-lioxabicyclo (2,2
[2] It relates to a method for producing an ester by reacting a bicyclo compound having an octane group (hereinafter simply referred to as a bicyclo compound) and an acid halide.

Conventionally, several types of bicyclo compounds have been investigated for use as stabilizers for vinyl chloride resins, herbicides, and the like. Recently, ring-opening isomerization polymerization of this type of compound using a cationic polymerization catalyst has been investigated, and a unique phenomenon in which the volume change accompanying polymerization is extremely small has been reported. It is attracting attention for its use in adhesives, etc. (Journal of Bolimar Science: Bolimar Letters Edition (J, Polym, Sc
i, ; Polym, Lett, Ed, ), 1
B, 457-459 (1980)) When a bicyclo compound is applied to such a polymerization-curable material such as a molding material, a casting material, or an adhesive, it becomes necessary to open the ring of the bicyclo compound.

As a ring-opening method for bicyclo compounds, a method using phenol, an organic polybasic acid, an organic polybasic acid anhydride, and a carboxylic acid type polyester (JP-A-58-109534 and JP-A-58-134113) is known. It is being

However, Fehir, organic polybasic acids, organic polybasic acid anhydrides, and carboxylic acid type polyesters have a slow ring-opening rate for bicyclo compounds, even in the presence of reaction accelerators such as boron trifluoride or tertiary amines. , the ring-opening reaction had to be carried out at a high temperature of 150 to 180°C.

Therefore, the present inventors have continued to develop a ring-opening method for bicyclo compounds under milder conditions that does not have the above drawbacks.

As a result, they discovered that acid halides exhibit extremely excellent activity in ring-opening of bicyclo compounds, and that acid halides simultaneously open the ring of bicyclo compounds and add to the bicyclo compounds to produce esters, thereby completing the present invention. reached.

That is, the present invention provides 2,6.7-)lioxabicyclo(
2,2] Bicyclo compounds having one or more octane groups in the molecule and acid halides having one or more acid halogen groups in the molecule (however, 2.6.7- in the bicyclo compounds)
This is a method for producing an ester, which is characterized by reacting a rioxabicyclo(2,2]octane group and an acid halide, except when the number of acid halogen groups in the acid halide is two or more.

The bicyclo compound used in the present invention is a compound having one or more 2,6,7-trioxabicyclo(2,2]octane groups in the molecule. Typical examples include compounds represented by the following general formula.

However, the meanings of the symbols in the above general formula are as follows.

m = integer I greater than or equal to 2? 1 = hydrogen atom; alkyl group (preferably 1 to 1 carbon atoms)
18 alkyl groups); cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl; benzyl,
Aralkyl groups such as phenylethyl, phenylpropyl and phenylisopropyl; aryl groups such as phenyl, biphenyl, xenyl and naphthyl; tolyl, xylyl,
Alkaryl groups such as ethylphenyl, propiophenyl, isopropiophenyl and butylphenyl; hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxyoctadecyl (preferably carbon atoms 1 to 18
hydroxyalkyl group); acetyloxymethyl, propionyloxymethyl, (1-propionyloxy)
Saturated and unsaturated group-substituted carbonyloxyalkyl groups such as ethyl, acryloyloxymethyl, methacryloyloxymethyl and (1-methacryloyloxy)ethyl;
Saturated and unsaturated group-substituted benzyloxyalkyl groups such as vinylbenzyloxymethyl; N-substituted carbamoyloxyalkyl groups such as N-ethylcarbamoyloxymethyl and N-phenylcarbamoyloxymethyl; vinyl, α-methylvinyl, β - Alkenyl groups such as methylvinyl, α-ethylvinyl, propenyl, octadecenyl; halogenated alkyl groups such as chloromethyl, bromomethyl, trichloromethyl, trifluoromethyl and h(1-7'lomo)ethyl;

R2 = hydrogen atom; alkyl group, cycloalkyl group, aralkyl group, aryl group, alkaryl group, hydroxyalkyl group, saturated and unsaturated group-substituted carbonyloxyalkyl group, saturated and unsaturated as shown for R8 above Substituted benzyloxyalkyl group, N-substituted rubamoyloxyalkyl group, halogenated alkyl group; Nitrogen-containing organic groups such as nitro group, dimethylamine group and amine group; Sulfur-containing group such as p-toluenesulfonyloxymethyl group Organic group; alkyloxycarbonyl group such as methoxycarbonyl and ethoxycarbonyl group.

R3a = aryl group such as a phenylene group Rffll and R5 = a polyvalent isocyanate compound or a reaction product of this and a polyhydroxy compound, from which at least m isocyanates have been removed from a urethane compound having a plurality of incyanate groups Group (hereinafter referred to as X); a group obtained by removing at least m epoxy groups from a polyepoxy compound (hereinafter referred to as Y); a group obtained by removing at least m acid halogen groups from a polyvalent organic acid halide; Yes (hereinafter referred to as Z).

R' = an organic group represented by the following general formulas (7), (8), and (9).

-NHCOOR9(7) -CJI (OH) CIIZOR9(8)COOR?
(9) [Here, R9
represents an alkylene group or an alkylidene group, preferably a group having 1 to 18 carbon atoms. ] R4 and R, = hydrogen atom; the same alkyl group, aralkyl group, cycloalkyl group as shown for R1 above,
Aryl group or alkaryl group. In addition, here m R4
are the same or different groups.

R, and R? =Hydrogen atom; the same alkyl group, aralkyl group, or aryl group as shown for R4 above. still,
Here, it is a group of the same type or different type as m R6.

■ = Polymer structural unit in which the unsaturated bond of an ethylenically unsaturated compound is cleaved.

(2)=Polymer structural unit in which the unsaturated bonds of the unsaturated group-substituted carbonyloxyalkyl group and the unsaturated group-substituted benzyloxyalkyl group are cleaved as specific examples for R1 above.

(2) = A polymer structural unit in which the unsaturated bond of an unsaturated group-substituted carbonyloxyalkyl group, an unsaturated group-substituted benzyloxyalkyl group, and an alkenyl group are cleaved, the specific examples of which are given for R8 above.

α and β = molar fractions of polymer constitutional units ■ and ■ or I and ■.

Most of the bicyclo compounds exemplified above are known and can be produced by various methods. For example, general formula (1)
Among the compounds represented by, R is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkaryl group, a halogenated alkyl group, or an alkenyl group, and R2 is a hydrogen atom, an alkyl group, or a cycloalkyl group. ,
Aralkyl group, aryl group, alkaryl group, hydroxyalkyl group, saturated and unsaturated group-substituted carbonyloxyalkyl group, saturated and unsaturated group-substituted benzyloxyalkyl group, N-substituted carbamoyloxyalkyl group, nitrogen-containing organic group, halogen an alkyl group, a sulfur-containing organic group, or
For compounds that are alkyloxycarbonyl groups,
Macromolecules
), 15.11-17 (1982), Journal of Polymer Science: Polymer Letters Edition
e: Polymer Letters of Po
polymer 5science: Polymer Le
tters Edition), ■, 457-459 (
1980), Journal of Organic Chemistry
stry), 1dan, 886-891 (1981),
Polymer Preprints Java (Polymer Pr
eprints, Japan), main 1.506 (19
B2L Journal of Polymer Science; Polymer Letters Edition (Journal of Pol
ymer 5science: Polymer Let
tersEdition), 1 main, 771-773 (
1980), Polymer Journal (Polymer J
local), 1st Sat., 485-488 (1982),
Polymer Journal
), 13U, 715-718 (1981), Macromolecules, 15, 217-
223 (1982) etc. One example is the dealcoholization reaction between a trialkyl orthoester represented by the following formula and a trimethylol compound represented by the following formula. can be manufactured in

(However, [1 and R12 represent the above-mentioned groups, and RIG represents an alkyl group.) This reaction is shown as follows.

Further, among the compounds represented by general formula (1), R1 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkaryl group, a hydroxyalkyl group, a saturated and unsaturated group-substituted carbonyloxyalkyl group, a saturated and unsaturated group-substituted benzyloxyalkyl group or a halogenated alkyl group, and R2 is a hydrogen atom, an alkyl group,
Bicyclo compounds that are cycloalkyl, aralkyl, aryl or alkaryl groups are described in the Journal of Organic Chemistry.
fOrganic Chemistry), 27
, 90-93 (1962), Journal of Medical Chemistry
al Chemistry), Yu 3, 1212-12
15 (1970), Dutch Patent 6.412.636
, and Polymer Preprints
It can also be synthesized by the method described in (1983) et al. As an example, it can be produced by a dehydration reaction between a carboxylic acid represented by the following formula and a trimethylol compound represented by the following formula (14'').

R", -COOHQ5) (However, R" and R"2 represent the above-mentioned groups.) This reaction is illustrated as follows.

-a Among the compounds represented by formula (1), bicyclo compounds in which R is an N-substituted carbamoyloxyalkyl group, bicyclo compounds in which R1 is a hydroxyalkyl group, and bicyclo compounds represented by the following formula 〇6) From monoisocyanate compounds, Polymer Journal
Journal), ■, 715-71
It is produced by a urethanization reaction according to the method described in J. B. (1981).

R,, -NCOQω (However, R11 is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or an alkaryl group.

) This reaction is shown below.

υ (However, R9 represents an alkylene group or an alkylidene group, preferably a group having 1 to 18 carbon atoms.) Furthermore, in the bicyclo compound represented by the general formula (1), R8 is a hydrogen atom, an alkyl group, or , is an aralkyl group, and R2
For bicyclo compounds in which is a hydroxymethyl group or a saturated group-substituted carbonyloxymethyl group, the following formula 0η
Pentaerythritol shown by and the following formula (15''')
It can also be produced by direct esterification reaction of monocarboxylic acids shown below.

H2O11 C1l□OH R” r Cool
(15') (However, R'' represents a hydrogen atom, an alkyl group, or an aralkyl group.) The charging composition ratio of pentaerytol and monocarboxylic acid is:
The latter is preferably 0.5 to 5 times the molar equivalent of the former, preferably 0.8 to 3 times the molar equivalent.

This reaction is expressed as follows.

This reaction uses an acidic catalyst, such as p-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, etc., to reduce the starting
．． It is generally carried out in the presence of 05 to 5% by weight.

The esterification reaction can be carried out in the presence or absence of a solvent.

Any solvent can be used as long as it is inert to the reaction raw materials, reaction products, and catalyst, but it is more preferable to use a solvent that can form an azeotrope with the water produced by the reaction. For example, aromatic hydrocarbons such as benzene, toluene, and xylene are preferably used.

After the esterification reaction is complete, if a solvent is used,
The solvent is removed from the reaction and the reaction is then slowly distilled under reduced pressure. Since a bicyclo compound is generated from the ester during distillation, adjustment of the internal temperature and degree of pressure reduction, and the shape of the distillation may be taken into consideration so as to appropriate the production rate and distillation rate of the bicyclo compound during distillation.

The bicyclo compound separated in this way is often a mixture of the following two types of bicyclo compounds.

However, by appropriately selecting the charging composition ratio of pentaerythritol and monocarboxylic acid, only one type can be selectively produced. For example, pentaerythritol:
When preparing propionic acid = 1:2.5 (mol ratio), 1-ethyl-4-propionyloxymethyl-2,6,7-trioxabicyclo[2,2,2,2
] Purely produced from octane.

In addition, by treating the above-mentioned mixed product with an alkali such as sodium methoxide, 1-R", -4
-Hydroxymethyl-2,6,7-dryoxabicyclo(2,2]octane is formed in pure form.

Next, the compound represented by the general formula (2) is itself a novel compound.The properties and typical manufacturing method of this novel compound are as follows.

The aryl group of R3A represented by the general formula (2) is not particularly limited and may be any known aromatic nucleus, but aromatic nuclei such as benzene, naphthalene, phenanthrene, anthracene, biphenyl, etc. are usually suitable. The general formula (2
], the bicyclo compound has two or more 2 in the aromatic nucleus.
．． 6.7-) is a compound having a rioxabicycloC2,2]octane group, of which many isomers are possible. However, due to steric hindrance, it may be difficult to manufacture the following bonding forms of the bicyclo compounds.

For example, 2,6,7-trioxabicyclo[2,2,2
] Those in which the octane groups are present at the ortho positions on the aromatic nucleus, or those in which the octane groups are present at the 9.10-position of anthracene and the 4.5-position of phenanthrene, respectively.

Further, the aryl group may contain a substituent.

In general, the substituent may be one that is inactive during the production of the bicyclo compound, and typical examples thereof include an alkyl group, a nitro group, and a halogen. Furthermore, the number of m in the general formula (2) varies depending on the type of aryl group, and is not particularly limited as long as it can be bonded, but is generally 2 to 5.
is the number that can be most easily combined.

The bicyclo compound can be confirmed to be the compound by the following measurements.

(1) Infrared absorption spectrum (IR) The presence of hydrogen on the 2.6.7-trioxabicycloC2,2]octane group and the aryl group can be confirmed.

Several absorption bands originating from the former appear between 1200 and 950 cm-', and absorption bands originating from the latter occur between 900 and 650 cm.
Several sharp lines appear at -'.

(2) 'H--nuclear magnetic resonance absorption vector ('H-
NMR) In deuterated dimethyl sulfoxide and deuterated chloroform solvents, σ (ppm) = 3.9-4.2 when measured with reference to tetramethylsilane.
A singlet absorption peak originating from the six methylene hydrogens in the 6.7-trioxabicyclo(2,2]octane group appears.Also, a singlet absorption peak derived from the six methylene hydrogens in the 6.7-trioxabicyclo(2,2)octane group appears. An absorption peak derived from hydrogen appears.Furthermore, the difference in the type of R4 in the general formula (2) is determined by the observation and analysis of the position and multiplicity of the absorption peak derived from hydrogen in R4, and the relative ratio of the absorption peak area. It can be determined by

When the areas of the three types of absorption peaks are measured as described above and the ratio is calculated, the value coincides with the ratio of the number of hydrogens bonded to each group.

(3) Mass spectrometry (MS) Molecular weight can be confirmed by using electron equilibration method (abbreviated as El method) and field desorption method (abbreviated as FD method) as means of mass spectrometry. When the molecular weight of the compound is M, a molecular ion peak is observed at the position M' or a pseudomolecular ion peak is observed at the position (M±1)0.

(4) Elemental analysis By comparing the analysis results of carbon and hydrogen with the theoretical values calculated from the general formula (2), rI! can be confirmed.

The bicyclo compound can be confirmed by the various measuring methods described above.

The bicyclo compound is a white crystalline solid at room temperature,
It has different physical properties depending on the substitution position. For example, the benzene nucleus has two 2.6.7-)lioxabicyclo(
2,2] Comparing the case where the octane group is in the meta position and the case where it is in the para position, the para form has inferior solubility compared to the meta form, and is soluble in small amounts in solvents such as methylene chloride, chloroform, and dimethyl sulfoxide. However, the meta-isomer is not only easily soluble in the above solvents (but also soluble in solvents such as benzene, toluene, xylene, acetone, and tetrahydrofuran).Furthermore, the meta-isomer has a melting point, When heated, para-isomers decompose at a certain temperature.Also, depending on the type of R4 in the general formula (2), they exhibit different physical properties such as solubility.The differences in these properties are as follows: Depending on the type mentioned above, it can be confirmed very easily using normal 111 verification means.

The method for producing the bicyclo compound represented by the general formula (2) is not particularly limited, and any method may be adopted.A concrete example of an industrially suitable method is as follows. That is, an orthoester of an aromatic polycarboxylic acid represented by the following formula 〇〇, (wherein R1°, R/, and R'''1° are the same or different alkyl groups. ) A bicyclo compound represented by the general formula (2) is produced by reacting with a trimethylol compound represented by the following formula.

The compound represented by formula G8) is a known compound, and is published in the Journal of Organic Chemistry (Jour
nal of Organic Chemistry)
, 117-13098-3102 (1962).

The reaction proceeds by dealcoholization as shown in the reaction formula below, and a bicyclo compound represented by the general formula (2) is produced.

Although the above dealcoholization reaction proceeds without the use of a catalyst, a catalyst is usually used to speed up the reaction rate. As the catalyst, any known catalyst used in dealcoholization reactions may be used without any restrictions. For example, an organic compound having a sulfonic acid group such as p-toluenesulfonic acid, sulfobutyric acid, sulfopropionic acid, or sulfuric acid is used as the catalyst. The amount of catalyst used is suitably used in the range of 0.01=10 wt%, preferably 0.1 to 5 wt%.

The reaction generally involves aromatic hydrocarbons, aliphatic hydrocarbons, or
Preferably, the reaction is carried out in an inert solvent such as a halogenated hydrocarbon. It is preferable that the above reaction proceeds while removing the alcohol produced by the reaction by evaporation, and therefore the above solvent preferably has a boiling point higher than that of the alcohol produced by the reaction.

Further, the reaction conditions can be selected from reduced pressure to increased pressure, and the reaction temperature can be selected from a range of 80 to 200°C as necessary.

The bicyclo compound represented by the general formula (2) produced in the above reaction is isolated as a solid by removing the solvent,
If necessary, it may be separated and purified by recrystallization from xylene, toluene, benzene, methylene chloride, or a mixed solvent of methylene chloride and benzene.

11 Among the compounds represented by formula (3), R311 is X and R' is represented by general formula (7), and among the compounds represented by general formula (4), R5 is X. , R'
Compounds represented by the general formula (force) are manufactured by the method described in Polymer Journal, Earthworks, 927-930 (1982), etc. One example is the following formula (H). )
A polyvalent isocyanate compound represented by and general formula (1)
Compounds (21) or (22) in which R1 or R2 is a monohydroxyalkyl group among the compounds represented by the formula (21) or (22) are produced by a method of subjecting them to a urethanation reaction.

X'-(-NGO),'
G! Φ [However, X' is a group obtained by removing (m'-m) isocyanate groups from X explained in R311 and R3, and m' is an integer of m or more. ] (However, R4, R6 and R1 are the groups as described above.) This reaction is shown as follows.

Among the compounds represented by the general formula (3), R311 is Y and R' is the compound represented by the general formula (8), and among the compounds represented by the -melon formula (4), R3 is Y, R'
Regarding the compound represented by the general formula (8), the following -
1 A polyepoxy compound having two or more epoxy groups in one molecule represented by the formula (23) and the general formula (21)
and a bicyclo compound having a monohydroxyalkyl group represented by (22).

[However, Y' is a group obtained by removing (m'-m) epoxy groups from Y explained for R3l+ and R3, and m
' is an integer greater than or equal to m. ] This reaction is shown below.

Among the compounds represented by general formula (3), R: lII is Z
Among the compounds in which R' is represented by the general formula (9) and the compound represented by the general formula (4), R5 is Z, and R
The compound represented by the general formula (9) is itself a novel compound. The properties and typical manufacturing method of this new compound are as follows.

That is, the new compounds are represented by the following formulas (3') and (4').

υ (However, Z, R, , R6, R7 and m are as described above.) This bicyclo compound can be confirmed to be the compound by the following measurements.

1) Infrared absorption spectrum (IR) 2.6. The presence of 7-1-lioxabicyclo(2,2]oftane group and ester bond (-C-C-) can be confirmed. The obi is 1100~900cm-'
Several bands appear in the 1700-18 absorption band derived from the latter.
One line appears strongly at 00cm-'.

2] 'H-Nuclear Magnetic Resonance Absorption Svector ('H-NMR)
When measured in deuterated chloroform solvent with reference to tetramethylsilane, 2.6.7-1-lioxabicyclo[2°2.2] was found at the position σ (ppm) = 3.8 to 4.1.
A singlet peak derived from the six methylene hydrogens in the octane group appears.

3) Mass spectrometry As mass spectrometry, electron equilibrium method (EI method) and field desorption method (
The molecular weight can be confirmed by using the FD method. When the molecular weight of the compound is M, a molecular ion peak is observed at the position m/e=M'' or a quasi-molecular ion peak is observed at the position (M±1)''.

4) Elemental analysis The carbon and hydrogen analysis results are expressed by the general formulas (3') and (4).
This can be confirmed by comparing it with the theoretical value calculated from ′).

The bicyclo compound can be confirmed by the various measuring methods described above.

The bicyclo compound is soluble in carbon tetrachloride, acetone, hexane, benzene, tetrahydrofuran, dioxane, chloroform, and methylene chloride;
) and (4') exhibit different solubility depending on the difference in ZSR, R6 and P.

Although any method can be used to produce the bicyclo compounds represented by the general formulas (3') and (4'), specific industrially advantageous methods are as follows.

That is, a bicyclo compound having a monohydroxyalkyl group represented by general formulas (21) and (22) and the following -JG
From polycarboxylic acid chloride represented by formula (24), Z'-(C-CA)m'
(24) [However, Z' is Z as explained in R2H and R3
A group obtained by removing (m'-m) acid chloride groups, where m' is an integer of m or more. ] In the presence of a base such as triethylamine or pyridine, the general formulas (3') and (4'
) is produced.

Examples of the polyhydric carboxylic acid chloride represented by the general formula (24) include sebacoyl chloride, adipoyl chloride, succinyl chloride, itaconyl chloride, glutaryl chloride, fumaryl chloride, malonyl chloride, oxalyl chloride, Phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetricarboxylic acid chloride, trans-3,6-endomethylene chloride 1.2
．． 3.6-titrahydrophthalic acid chloride and trans-1,2-cyclobutanedicarboxylic acid chloride are preferably used.

The dehydrochlorination reaction is carried out in an inert solvent in the presence of a base such as triethylamine or pyridine.

The composition ratio of the raw materials is equal moles of 2.6.7-trioxabicyclo (2,2,2:l octane group and acyl chloride group) in the bicyclo compound, or 0.8 to 0.8 to 0.8 to 1 mole of one of the acyl chloride groups, if necessary. It is preferable to use it in a range of 1.2 times equivalent.

As the inert solvent, carbon tetrachloride, dioxane, tetrahydrofuran, methylene chloride, chloroform, benzene, etc. are used, and it is preferable to use them in an amount of 2 to 10 times the volume of the reaction substrate. Further, triethylamine and pyridine are used in an amount of 1 to 5 times, preferably 1 to 5 times, relative to the acyl chloride group.
It is better to use ~3 equivalents.

Although the reaction can be carried out at any temperature from water cooling to the boiling point of the solvent, it is generally preferable to carry out the reaction at a temperature in the range of room temperature to 100°C. The degree of progress of the reaction can be examined by various methods, including thin layer chromatography using an appropriate solvent.

After the above reaction, the reaction solution is filtered and concentrated to produce bicyclo compounds represented by the general formulas (3') and (4'). Furthermore, if necessary, extraction and purification using hexane, heptane, ether, etc., and decolorization treatment using activated carbon can be carried out.

The bicyclo compounds represented by the general formulas (5) and (6) are described in Polymer Journal (Polymer Journal).
al), Jodo, 485-488 (1982), Journal of Polymer Science: Polymer Letters Edition (Journal of Polymer 5
science :Polymer Letters E
dition), 1 main, 771ゞ773 (198
0) and the method described in JP-A No. 58-61109.

That is, in the compound represented by the general formula (1), R or R2 is a bicyclo compound having a radically polymerizable unsaturated group, or a bicyclo compound produced by radical polymerization of this with another ethylenically unsaturated compound. .

For example, by carrying out bulk polymerization of a bicyclo compound in which R3 is an ethynyl group among the compounds represented by the general formula (1) using, for example, ditertiary butyl peroxide as a radical initiator, the above general formula (6) can be obtained. A compound represented by is produced. This reaction is shown below.

Rz RzAlso, the general formula (
The above-mentioned general A compound represented by formula (5) is produced.

Furthermore, as a method for producing the bicyclo compounds represented by the general formulas (5) and (6), production is performed by a polymer reaction in which a polymer having a functional group is reacted with a bicyclo compound having a functional group that is reactive with the functional group. be done.

For example, the following formula (2
The bicyclo compounds represented by the general formulas (5) and (6) are produced by subjecting the bicyclo compounds represented by 5) or (26) to a polymer reaction according to a conventional method for this reaction.

-i Specific examples of ethylenically unsaturated compounds that can constitute the unit (■) in the bicyclo compounds represented by formulas (5) and (6) include vinyl acetate, acrylonitrile,
Thymel methacrylate, chloromethylstyrene, styrene, etc. may be used alone or in combination. α and β, which are the molar fractions of the units ■ and ■ or ■, can take any value β≠0.

The bicyclo compound explained above is ring-opened by the acid halide mentioned later.

As the acid halides, known ones having one or more acid halogen groups in the molecule can be used without any restrictions. Typical examples of such acid halides include carboxylic acid halides, organic phosphoric acid halides, and organic sulfonic acid halides, and these acid halides are preferably used in the present invention.

Specific examples of these acid halides are as follows.

(1) (A) I-dichloroacetyl chloride, dichloroacetyl chloride, bromoacetyl chloride, bromoacetyl bromide, chloroacetyl chloride,
Acetyl bromide, acetyl chloride, acetyl iodide, α-bromopropionyl bromide, β-
Chloropropionyl chloride, propionyl chloride, heptafluoro-n-butyryl chloride, α-bromo-n-butyryl bromide, α-promoisobutybromide, γ-chlorobutyryl chloride, isobutyryl bromide, n-butyryl Chloride, isobutyryl chloride, valeroyl bromide, isovaleroyl chloride, pivaloyl chloride, n-valeroyl chloride, n-caproyl chloride, cyclohexanecarbonyl chloride, enansyl chloride, 0-nitrophenoxyacetyl chloride, p- Chlorophenoxyacetyl chloride, phenylacetyl chloride, phenoxyacetyl chloride, n-capryl chloride, 2-ethylhexanoyl chloride, 2-n-propyl-n-valeroyl chloride, 2-phenoxypropionyl chloride, belargonyl chloride, 3,
5.5-trimethylhexanoyl chloride, n-capryl chloride, l-adamancune carbonyl chloride, lO-undecenoyl chloride, n-undecanoyl chloride, L-menthoxyacetyl chloride,
1 which does not have a double bond or an aromatic nucleus in the alpha position, such as n-dodecanoyl chloride, myristoyl chloride, balmitoyl chloride, γ-lylnoyl chloride, lyluoyl chloride, oleic acid chloride, cis-β-tocosenoyl chloride, etc. carboxylic acid halide.

(B) oxalyl chloride, succinyl chloride,
Glutaryl chloride, adipoyl chloride, azeroyl chloride, sebacoyl chloride, malonyl chloride, oxalyl bromide, trans-3,6-
Polyvalent carboxylic acid halides that do not have a double bond or aromatic nucleus at the α position, such as endomethylene-1,2,3,6-titrahydrophthaloyl chloride, trans-1,2-cyclobutanedicarboxylic acid chloride, etc. .

(C) Acryloyl chloride, crotonoyl chloride, crotonoyl bromide, methacryloyl chloride, 2-thenoyl chloride, 3,5-dinitrobenzoyl chloride, 2-chloro-4-nitropenzoyl chloride, 2-chloro-5-nitrobenzoyl chloride , 2,4-dichlorobenzoyl chloride, 3,4-
Dichlorobenzoyl chloride, 3,5-dichlorobenzoyl chloride, m-bromobenzoyl chloride,
p-bromobenzoyl chloride, 0-fluorobenzoyl chloride, m-nitrobenzoyl chloride, p
-Nitrobenzoyl chloride, m-chlorobenzoyl chloride, 0-chlorobenzoyl chloride, p-chlorobenzoyl chloride, benzoyl bromide, benzoyl chloride, benzoyl fluoride, m-)
lyoyl chloride, 0-) lyoyl chloride, p-
Toluoyl chloride, O-methoxybenzoyl chloride, p-methoxybenzoyl chloride, cinnamoyl chloride, α-naphthoyl chloride, β-naphthoyl chloride, P-phenylazobenzoyl chloride, anthraquinone-β-carbonyl chloride, trimellitic anhydride Monovalent carboxylic acid halides having a double bond or aromatic nucleus in the α-position, such as chloride, furoyl chloride, etc.

CD) A double bond or aromatic nucleus at the alpha position such as furoyl chloride, isophthaloyl 1 chloride, phthaloyl chloride, terephthaloyl chloride, itaconyl chloride, trimellitic acid chloride, 1,3,5-benzenetricarboxylic acid chloride, etc. A polyvalent carboxylic acid halide having

(E) N,N-dimethylcarbamoyl chloride, N
, N-diethylcarbamoyl chloride, N,N-diphenylcarbamoyl chloride and the like, carboxylic acid halides in which the α-position is a nitrogen atom.

(n) β-Chloroethylphosphosonic acid dichloride, benzenephosphonyl dichloride α-naphthylphosphoryl chloride, diphenylphosphoryl chloride, O-phenylene phosphorochlorate, phosphozinc chloride O-phenylene chloride, phenylphosphoryl dichloride and p-chloroanilide Organic phosphoric acid halides such as phosphoryl dichloride.

(■) Trichloromethanesulfonyl chloride,
Chloromethylsulfonyl chloride, methanesulfonyl chloride, ethanesulfonyl chloride, isopropylsulfonyl chloride, 1-propanesulfonyl chloride, 1-butanesulfonyl chloride, 2,4.5-trichlorobenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, benzenesulfonyl chloride , toluene-3+4-cisulfonyl chloride, benzylsulfonyl chloride, 0-toluenesulfonyl chloride, p-toluenesulfonyl chloride, p-acetaminobenzenesulfonyl chloride, p-ethylbenzenesulfonyl chloride, p-xylene-2-sulfonyl Organic sulfonic acid halides such as chloride, 1-octanesulfonyl chloride, 2-mesitylenephonyl chloride, α-naphthalenesulfonyl chloride and β-naphthalenesulfonyl chloride.

Among the acid halides exemplified above, carboxylic acid halides are preferable because they have a high ring-opening rate of the bicyclo compound described above and produce a large amount of ester.

Generally, the acid halides mentioned above tend to be unstable and difficult to handle if the bicyclo compound has a high ring opening rate. For example, acid bromide has a higher ring opening rate than acid chloride, but acid chloride is more stable and easier to handle. In addition, acid halogen compounds that do not have a double bond, aromatic nucleus, or nitrogen atom at the α position, acid halides that have a double bond or aromatic nucleus at the α position,
The ring opening rate of bicyclo compounds decreases in the order of acid halides having a nitrogen atom at the α-position, but conversely, the stability increases.

Among acid halides, bicyclo compounds which have a high ring opening rate but are unstable are preferably used by dissolving them in a solvent, as described below, in order to improve stability.

When a solvent or the like is not used, an acid halide having a double bond or an aromatic nucleus at the α-position, which has a relatively high ring-opening rate and good stability, is preferably used.

Among the combinations of reactions between the bicyclo compound and the acid halide described above, the number of 2,6,7-trioxabicyclo(2,2]octane groups in the bicyclo compound and the number of acid halogen groups in the acid halide are both 2. In other words, the reaction combination of a bicyclo compound and an acid halide in the present invention is 2,6.7-1
-1 rioxabicyclo(2,2]octane group in the molecule
A combination of a bicyclo compound having two or more acid halide groups and an acid halide having one or more acid halide groups in the molecule, and 2,6.7
There are two combinations: a bicyclo compound having two or more -trioxabicyclo(2,2]octane groups in the molecule and an acid halide having one acid halide group in the molecule.

In the reaction between the bicyclo compound and the acid halide described above, the acid halide opens the ring of the bicyclo compound and is added to the bicyclo compound to produce an ester, as shown in the reaction mechanism described below.

The reaction between a bicyclo compound and an acid halide can be carried out by simply mixing these compounds.

The method for mixing the bicyclo compound and the acid halide is not particularly limited, and any known method may be employed. Examples of suitable mixing methods are as follows.

■ If the bicyclo compound and acid halide are in liquid form, a method in which they are mixed directly.

(2) When at least one of the substances is solid and has a unique melting point, the two are mixed by heating above that temperature and melting the two.

■ When one is liquid and the other is solid, a method of dissolving the solid substance in the liquid substance and mixing the two.

■ If one of the solids is liquid or can be liquefied above a specific temperature and the other cannot be liquefied, a method in which the solid is decomposed into the liquid and mixed in a non-homogeneous system.

■ If both are solids, a method is to mix them in a solid phase by grinding, kneading, etc. in a state in which they coexist.

■ A method of mixing solids and liquids in a dissolved state using an appropriate solvent.

The solvent used in the above (2) is preferably a solvent that is inert to bicyclo compounds and acid halides.

Generally, an appropriate solvent is selected depending on the use of the ester, which is a ring-opening product of a bicyclo compound of the present invention with an acid halide. Examples include low boiling point compounds such as ethyl ether, acetone, chloroform, methylene chloride, carbon tetrachloride, heptane, hexane, pentane, octane, cyclohexane, cyclopenkune, benzene, toluene, xylene, ethyl benzoate, tetrahydrofuran, dioxane, and ethyl acetate. Active solvents and polymerizable monomers such as styrene, methyl methacrylate, methyl acrylate, hynyl acetate, acrylonitrile, and ethylene glycol dimethacrylate are generally used. Although the acid halides mentioned above are unstable, they can be made to exist stably by using a solvent. Therefore, the method using a solvent is
This is a preferred method because the acid halide can be easily handled.

In the method for producing esters of the present invention, the blending ratio of the bicyclo compound and acid halide depends on the ring-opening reaction conditions, the use of the ester that is the ring-opening reaction product, the type of additives, etc.
It can be selected as appropriate, but for boat fishing, the acid halogen group is preferably 0.5 to 2 equivalents to the 2,6.7-)lioxabicyclo(2,2]octane group, preferably 0.7 to 1.3 times equivalent amount is used.

The method for producing an ester of the present invention can be carried out in any manner depending on the use of the ester, which is a ring-opening reaction product. For example, when used as an adhesive, it can be applied to an adherend surface and the adherends brought into contact with each other. When used as a molding material, it can be poured into a mold.

The optimum conditions for carrying out the ring-opening reaction vary depending on the type of bicyclo compound and acid halide used, but are usually O'C to 250 °C, preferably 15 °C to 150 °C.
The reaction may be carried out at a temperature of from several minutes to several hours.

The method for producing an ester of the present invention can also be carried out when the following substances are simultaneously present in addition to the bicyclo compound and the acid halide.

(1) A cyclic compound copolymerizable with a bicyclo compound such as an epoxy compound, a spiro-orthoester compound, a lactone, an acid anhydride, and a cyclic ether as a ring-opening reaction rate regulator.

(2) Glass fiber, carbon fiber, as a filler for composite materials,
Fillers such as quartz, aluminum powder, spherical alumina, spherical silica, polymethyl methacrylate, polyvinyl chloride, polyethylene and polypropylene.

The mechanism of the ring-opening reaction of bicyclo compounds with acid halides is not yet clear, but when a carboxylic acid chloride is used, the ring-opening reaction occurs according to the reaction of the following formula, based on the results of infrared absorption spectra and nuclear magnetic resonance absorption spectra. It is thought that it undergoes ring isomerization.

When ring-opening isomerization of the above-mentioned bicyclo compound with an organic polybasic acid, an organic polybasic acid anhydride, phenol, etc. based on the conventional method G, as shown in specific gravity example 1 described later, the reaction was extremely high. (low rate), the addition of promoter 1 is essential. For example, i 1, 4-diethyl-2,6,7-trioxabicyclo[2,2,2]octane, acetic acid, n-caprylic acid, 0-ethoxybenzene, fragrant acid, ethyl salicylate, acetic anhydride, and 4-methylhexahydrophthalic anhydride) at 150°C for 14 hours, the ring-opening reaction rate in each case was 46.22.17.2
．． They were 0 and 0%. In addition to the above compounds, alcohols such as trichloroethanol, aldehydes such as salicylaldehyde, organic acid esters such as triethyl phosphite, methyl benzoate, and diethyl malonate, and noamines such as triethanolamine and trimethylene diamine , isocyanates such as tolylene diisocyanate, nitriles such as acetonitrile, halogen compounds such as hexachlorocyclopentadiene, organometallic compounds such as tetrabutoxytitanate, and epichlorohydrin, tetrahydrofuran, thiophene, tetrahydrobilane, ε-
When a 3- to 7-membered ring organic compound such as cabrolactone was used, ring opening of the bicyclo compound hardly proceeded.

On the other hand, when using propionyl chloride, which is an acid halide compound, 100% at 100°C for 2 hours and 60°
The reaction rate was 54% in C2 hours, and when oxalyl chloride and propionyl bromide were used, a surprisingly high reaction rate of 100% in 2 hours at room temperature was shown.

That is, it is clear that organic acid halides are highly active compounds that are specific as ring-opening reagents for bicyclo compounds.

Compared to conventional ring-opening methods for bicyclo compounds, the method of the present invention is characterized in that the ring-opening reaction of bicyclo compounds proceeds without the addition of promoters, etc., and moreover, in a shorter period of time under milder conditions. It has the advantage of being able to open the ring in a short amount of time. Furthermore, it has the characteristic that an ester, which is a ring-opening product, can be obtained without volumetric shrinkage or with an extremely small volumetric shrinkage rate.

Therefore, the method of the present invention is an extremely effective method that can be used in various fields of casting materials, molding materials, composite materials, adhesives, and coatings.

EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, Production Examples, and Comparative Examples, but the present invention is not limited to these Examples.

In addition, in the following examples, the bicyclo compounds shown in Table 1 below and the bicyclo compounds produced in Production Examples 1 to 9 were used. The bicyclo compounds shown in Table 1 were synthesized by the known method described above.

Table-1 Table-1 (continued) Table-1 (continued) Table-1 (continued) Production example-1 2.04 g (0,0071 mol) of trimethyl orthoisophthalate, 1.91 g of trimethylolpropane in a 30 cc eggplant flask. (0,0143mo
1), P-) 0.03 g of luenesulfonic acid and 20 g of xylene were added, a technical fractionating head, a temperature gauge, a cooling pipe, and a receiver were attached to this, and the temperature of the reaction solution was gradually raised while stirring. Heated to 100-120°C. Distillation of methanol began as the temperature rose, and after about 10 minutes, about 1.7 cc of distillate containing methanol as a main component was obtained. Thereafter, the reaction solution was air-cooled, and after cooling, 0.05 g of triethylamine was added to neutralize the acid. Next, the product was recrystallized from the reaction solution and isolated to obtain 1.84 g of white needle-like crystals. The yield was 72%.

The physical properties of the white crystalline solid thus obtained were as follows.

(1) Melting point 149-152°C (2) Infrared absorption spectrum 1120.1095.1005 and 995c1n-' (
3) 'H4A'' magnetic resonance spectrum measurement solvent: deuterated chloroform Standard: tetramethylsilane (4) Mass spectrometry El method m/e = 362 (M'') (5) The following bicyclo compound [23] was obtained by elemental analysis or above. was manufactured.

Production Example-2 In a 30cc eggplant flask, 2.0 g (0,0070 mol) of trimethyl orthoisophthalate and 1.68 g (0,0140 mol) of trimethylolethane were placed in a 30 cc eggplant flask.
), 0.03 g of P-toluenesulfonic acid and 20 g of xylene were added, a skimmed fractionator head, a temperature gauge, a cooling pipe and a receiver were attached to this, and the temperature of the reaction solution was gradually raised while stirring, until the temperature reached 100 g. Heated to ~120°C. As the temperature rose, the reaction solution became cloudy and methanol stopped distilling out. After reacting for about 10 minutes, distillate containing methanol as the main component 1.7
I got cc. Thereafter, the reaction solution was air-cooled, and after cooling, 0.05 g of triethylamine was added to neutralize the P-)luenesulfonic acid, and stirring was stopped. The reaction solution was then filtered to obtain a white precipitate.

This was recrystallized from methylene chloride to obtain 1.67 g of a white crystalline solid. The yield was 72%.

The physical properties of the white crystalline solid thus obtained were as follows.

(1) Melting point 250-251'C (2) Infrared absorption spectrum 1120.1100.1000 and 980 cm-'H (3) 'H-Nuclear magnetic resonance absorption spectrum' Measurement solvent: Deuterium chloroform Standard: Tetramethylsilane (4) Mass spectrometry EI method m/e=334 (M'') (5) Elemental analysis The following bicyclo compound [24] was produced by the above method.

Production Example-3 Bicyclo compound (8) in Table-1 18.8g (0,
111 Iol), pyridine 8.69 g (0.11 m
ol) and 50 cc of carbon tetrachloride were placed in a 300 cc Z-Low flask equipped with a dropping funnel and a nitrogen inlet tube. After purging the inside of the flask with nitrogen, 9.15 g of adipoyl chloride (
A mixed solution of 0.05 mol) and carbon tetrachloride was added dropwise over about an hour. After the addition was completed, the mixture was kept at 70°C overnight with stirring. It was then filtered, and the filtrate was freed of solvent using an enoma borator. Next, the residue was extracted with hexane, and the extract was concentrated to obtain a colorless and transparent liquid. Yield is 7
It was 8%. Various measured values of the viscous liquid obtained in this manner were as follows.

(1) Viscosity 1341 poise (23°C) (2) Infrared absorption spectrum 1740 cm-” (νcmo) 1105.10
25.1000 (3) 'H-Nuclear magnetic resonance absorption vector measurement solvent-
Deuterium chloroform standard: Tetramethylsilane (4) Elemental analysis The following bicyclo compound [25] was produced by the method described above.

Production Example-4 Bicyclo compound (8) in Table-1 18.8g (0,
10111ol), pyridine 8.69g (0,11
mol ) and 50 cc of carbon tetrachloride were placed in a 300 cc 20 flask equipped with a dropping funnel and a nitrogen introduction tube. After replacing the inside of the flask with nitrogen, while stirring magnetically,
Sebacoyl chloride 11.96g (0,
05 mol) was added dropwise over about 1 hour. After completion of the dropwise addition, the mixture was stirred at 70°C day and night. Thereafter, it was filtered, and the solvent was removed from the filtrate using an evaporator. Next, the residue was dissolved in carbon tetrachloride, and activated carbon was added to this solution and stirred for about 2 hours. Thereafter, the solution was filtered and concentrated using an evaporator to obtain 19.52 g of a colorless and transparent viscous liquid. Yield is 72%
Met.

Various measurements of the viscous liquid thus obtained were as follows.

(1) Viscosity 164 voids (23°C) (2) Infrared absorption spectrum 1730 cm-' (C-10) 1100.10
20.1000 (3) 'H-Nuclear Magnetic Resonance Svector Measurement Solvent Double Chloroform Standard: Tetramethylsilane (4) Elemental Analysis The following bicyclo compound [26] was produced by the above method.

Production Example 5 According to the methods of Production Examples 3 and 4, the bicyclo compounds shown in Table 2 were produced.

Production Example-6 1.06 g of bicyclo compound (15) shown in Table-1,
45.211 g of di-tert-butyl peroxide was placed in an ampoule, and then nitrogen gas was bubbled through it for 5 minutes. Thereafter, the ampoule was degassed using a vacuum pump while being cooled in dry ice. After degassing, the ampoule was sealed.

The sealed ampoule was heated in a 120'C oil bath for 24 hours. After the reaction, the ampoule was broken, about 2 cc of dichloromethane was added to dissolve the contents, and then precipitated into hexane. The precipitate was filtered and dried. The polymer thus obtained was the following bicyclo compound [31]. The yield was 0.69 g, and the yield was 62.4%.

+CHz CHstHs Production Example-7 Bicyclo compound (12) Ig shown in Table-1, 4 g of dimethylformamide, and 6 azobisisobutyronitrile
．． 8 mg was taken into a test tube and then nitrogen was bubbled through for 5 minutes. Thereafter, the test tube was tightly stoppered, and the reaction was then carried out in a 70°C oil bath for 1 hour. After the reaction, the contents were precipitated in methanol, filtered, and dried to obtain 0.59 g of a white powder polymer. Ta. The polymer thus obtained was the following bicyclo compound [32].

CH.

1+CH, -C-→- Police station C=0 C.I.

Js Production Example-8 Bicyclo compound (22) shown in Table-1 2.42g, methyl methacrylate 1.00g, dimethylformamide 5
32.8 mg of azobisisobutyronitrile and 32.8 mg of azobisisobutyronitrile were taken into an ampoule, and then nitrogen gas was bubbled through it for 5 minutes. Thereafter, the ampoule was degassed using a vacuum pump while being cooled in dry ice.

After degassing, the ampoule was sealed. Next, the ampoule is 70°
C. Heated in an oil bath for 15 hours. Then, after breaking the ampoule and adding 5 cc of methylene chloride to the contents,
The content liquid was precipitated in a tetrahydrofuran-hexane mixed solution. After filtration and evaluation, about 2 g of a white polymer was obtained.

The thus obtained polymer was confirmed by elemental analysis and NMR measurement to be a bicyclo compound [33] having the following structure.

I Cl1j CH2ztls Structure Example-9 4.25 g of the bicyclo compound (15) shown in Table 1, 1.33 g of acrylonitrile, and 0.21 g of di-tert-butyl peroxide were placed in an ampoule. After bubbling nitrogen gas for 5 minutes, the ampoule was degassed while being cooled in dry ice. After degassing, the ampoule was sealed. The ampoule was then heated in a 70°C oil bath for 24 hours. After the reaction, break the ampoule and add 5 cc of methylene chloride.
was added and mixed and dissolved with the contents, and then precipitated in hexane. The precipitate was filtered and dried to obtain 2.1 g of a white powdery polymer. The polymer obtained in this way is
By elemental analysis and NMR measurement, it was confirmed that it was a bicyclo compound [34] with the following structure.

Js Examples 1 to 42 and Comparative Examples 1 to 8 The bicyclo compounds shown in Table 1 were placed in an ampoule having a volume of 5 cc, and then the acid nitride compounds shown in Table 3 were added to 2.
6.7-) Lioxabicyclo(2,2]octane group and acid halogen group were taken in equal equivalent weight.

Next, the ampoule was sealed, and a ring-opening reaction was carried out under the conditions shown in Table 3. After the reaction, the ampoule was broken, the contents were taken into a sample tube for nuclear magnetic resonance spectroscopy measurement, and a nuclear magnetic resonance absorption spectrum was measured using deuterated chloroform as a solvent and tetramethylsilane as a standard. The ring opening rate is 3.8 to 4.2 ppm based on the 6 methylene protons in the 2,6.7-dryoxabicyclo(2,2]octane group on the nuclear magnetic resonance spectrum. It was determined from the rate of decrease in the integral value of the line.

As a comparative example, a reaction was carried out in the same manner as above using the reaction reagents shown in Table 3 in equimolar amounts to the bicyclo compound, and the ring opening rate of the bicyclo compound was determined. The results are also listed in Table-3.

Table 3 (Continued) Examples 43 to 53 The bicyclo compounds shown in Table 1 were placed in an ampoule with a volume of N 5 cc, and then the acid halides shown in Table 4 were added to 2.
6.7-) Lioxabicyclo(2,2]octane group and acid halogen group were taken in equal equivalent weight.

Next, the ampoule was sealed, and a ring-opening reaction was carried out under the conditions shown in Table 4. After the reaction, the ampoule was broken, the contents were taken out, and the infrared absorption spectrum was observed. The degree of ring opening is 2.6.7-1- on the infrared absorption spectrum.
Based on the lioxabicyclo(2,2,2]octane group<
Evaluation was made from the degree of decrease in absorption of several lines between 1200 and 900 cm-'. As a result, reaction products as listed in Table 4 were obtained, and it was confirmed that the absorption based on each bicyclo compound in the infrared absorption spectrum disappeared in all cases. From this, it was found that the ring opening rate of the bicyclo compound reached almost 100%.

Examples 54 to 68 Bicyclo compound [3] shown in Table 1 was placed in an ampoule of volume ffl 5 CC, and then acid halides shown in Table 5 were mixed in the proportions shown in Table 5. added. Next, the ampoule was sealed, and a ring-opening reaction was carried out under the conditions shown in Table 5. After the reaction, the ring opening rate of the bicyclo compound was determined in the same manner as in Examples 1 to 42. The results are also listed in Table-5.

Examples 69 to 74 The bicyclo compounds produced in Production Examples 6 to 9 were each
Take 1 g each into test tubes and add 15 cc of chloroform to each.
was added and dissolved. To this solution, an acid chloride compound as shown in Table 6 was added so that the acid chloride group and the 2,6,7-dolioxabicyclo(2,2]octane group were in equal equivalent amounts.Next, the test tube was It was tightly capped and heated at 60°C for 15 hours. After the reaction, the contents in the test tube were taken into a sample tube for nuclear magnetic resonance spectrum measurement, and the nuclear magnetic resonance spectrum was measured using tetramethylsilane as a standard. Ring opening rate is a sharp singlet of <3.8 to 4.2 ppm based on the six methylene protons in the 2,6.7-)lioxabicyclo(2,2]octane group on the nuclear magnetic resonance spectrum. It was calculated from the rate of decrease in the integral value.

The results are also listed in Table-6.

Claims (1)

[Claims] (1) 2,6,7-trioxabicyclo[2,2,2]
Bicyclo compounds having one or more octane groups in the molecule and acid halides having one or more acid halogen groups in the molecule (However, 2,6,7-trioxabicyclo[2,2,2] in the bicyclo compounds) 1. A method for producing an ester, which comprises reacting an octane group and an acid halide (excluding cases where the number of acid halogen groups in the acid halide is two or more).