JPS6064946A - Tricyclo(5.2.1.02,6)dec-8-ene-3,4-dicarboxylic acid diester and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is alkyl, unsaturated alkyl or cycloalkyl). EXAMPLE:Dimethyl tricyclo[5.2.1.0<2>,<6>]dec-3-ene-8,9-dicarboxylate. USE:A precursor for resin fields such as epoxy hardeners or polyester resins, etc. agricultural chemicals such as antimicrobial agents, herbicides, etc. and medicines such as central nervous action agents or circulatory action agents, etc. and expected as a raw material or intermediate for coating materials having particularly heat resistance, electrical characteristics, solubility in solvents, etc. adhesives, plasticizers for polyvinyl chloride. PREPARATION:Dicyclopentadiene of formula II is reacted with CO, an alcohol expressed by the formula ROH and/or an acetal, ketal or alkyl orthoformate which is a derivative thereof in the presence of a Pd catalyst, copper or an iron compound and/or O2 and diesterified directly to afford the aimed compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides tricyclo(5,2,1,02.6)de8-ene-
This article relates to 3,4-dicarboxylic acid diesters (representing Rid alkyl, unsaturated alkyl, and cycloargyl) and their production method.

The compound of the present invention is a new compound, and is generally used in the field of resins such as this type of dicarbonate, epoxy thermosetting agents, polyester resins, etc., agricultural chemicals such as antibacterial agents and herbicides, central nervous system active agents, and circulatory agents. As a precursor for pharmaceuticals such as active agents.

Its application fields are extremely wide-ranging.

Especially in the field of resins, paints and adhesives have characteristics such as heat resistance, electrical properties, and solubility in If agents.

J41J is expected to be used as a raw material or intermediate for vinyl chloride plasticizers, etc. Furthermore, regarding polyimide, the present inventors have filed a patent application (%
(Report No. 114914/1982).

The compound of the present invention can be produced by two routes represented by the following formula.

11) Tricyclo[5,2,1,02・6]des-8-en-
6,4-Dicarboxylic acid diester (abbreviated as TODB) 2) (TODE) (TODC) (TODB) Tricyclo(s, 21.o2.6"guse-8-
En-6,4-dicarbo7 fi2 (abbreviated as TCIJO)
(R': alkyl different from R, unsaturated alkyl,
Indicates a cycloalkyl group. ) That is, (1) a method using a direct diesterization method of dicyclopentadiene. (2) TOD obtained by diesterification]
After hydrolyzing n to obtain TODC, esterification with an alcohol different from the alcohol used for diesterification yields T.
OD, FIEL) method.

It is.

Hereinafter, the first method for diesterification of dicyclopentadiene will be explained.

Traditionally, the direct diester ratio of cycloolefins t, j,
J, K, 5tille
), etc. in the Journal of the American Chemical Society (J, Am, C!hem, Sac,) 9
Vol. 8, No. 7, p. 1810 (, 1976) Only a few studies have been conducted on VC cyclomonoolefins, and the number is extremely small.

The inventors of the present invention have conducted extensive dissections on a method for selectively and directly diesterizing one double bond of dicyclopentadiene, a cyclodiolefin, as a raw material. discovered a reaction that completely selectively diesterifies only the double bond of the 7-clopentene ring in high yield while leaving the double bond of the norbornene ring.

This has led to the completion of the present invention.

Dicyclopentadiene, which is the raw material of the present invention, is contained in a considerable proportion in the C5 fraction obtained by cracking naphtha, and since there is currently a large amount of residual N: It can be said that the implications are extremely large. The diesterization of the present invention is based on the basic V-[Pd2+
Palladium is generally used as a catalyst, but the diesterification reaction proceeds even in the absence of radium.
I also found The form of palladium is as follows:
I 1 Iso 1 Volume Salt, J" ↓ Somatic Paragiuno, Colloidal Gold I
s ”J: Its form is 1; It can be used without being restricted.Specifically, baladium chloride, palladium nitrate, (j:jt'r2 palladium, il'p acid](
radium.

Propion city palladium, baradium, - carbon.

Palladium-7 Lika, Balajiu L-Alumina.

Palladium-barium carbonate, vandium black, colloidal palladium, etc. can be obtained.

The amount of infarction is 01 for the raw material synclopentagene.
If the molar ratio is higher than that, diester can be obtained in high yield.

Zara Vko9 In the water reaction, Pc12+ becomes Pd0 due to the reaction and becomes thinner, so return this to pt > 24 1 tribute fhi 11
1] is reassuring. As the oxidizing agent, a small metal compound with a redox position of 11 is preferable, and G'V(-iiM
] Also, one iron compound is used.

For specific vc, cupric chloride, nitric acid ≦I”l + j
l:f cupric acid, 411Ll cupric formate, ferric chloride.

Ferric nitrate, ferric sulfate, ferric chloride, ferric vinegar, etc. are used, and especially copper compounds give excellent results. Furthermore, in any of these compounds rJ, the diester is produced in a higher yield in the hydrothermal form (1), and the yield tends to decrease in the hydrated form.

1 History of these oxidants, raw material VC theory +
= Indispensable and 9 In the diesterification reaction of the present invention, +1 palladium catalyst is so-called! to 1:h (if bait month 4,
It is necessary to use 2 moles of the raw material synchropentagene.

On the other hand, it is also possible to use molecular oxygen as an oxidizing agent without using a metal compound, and it is also possible to use a combination of a metal compound and molecular oxygen.

In addition, when using 9 molecular oxygen as an abrasion agent, use methyl orthoformate, which is also an alcohol derivative.

Ortho (i'l: rR methyl, ortho Q ethyl, 1.
It is important to add dehydrated Mll such as 1-dimethoxycyclohexane, which results in a significant yield improvement.

In addition, in accordance with the present invention, it was unexpectedly discovered that the oxidative addition reaction occurs even when the metal compound alone is used as a VCCa-forming agent, and the diesterification reaction proceeds. Under these conditions, the reaction rate is lower than in the case of a combination of palladium and gold 4'A (hypolysate), but the selectivity to the desired diester is high.

Therefore, there is a possibility that it can be an effective condition for industrial IfC to reduce the independent cost.Alkyl alcohol, unsaturated f
l+alkyl alcohol, cycloalkyl alcohol,
Benzene shield, substituted alkyl alcohol, benzene substituted unsaturated alcohol, alkyl and unsaturated alkyl are CI N
It may contain atoms, and it does not matter whether it is a monohydric alcohol or a polyhydric alcohol.

Specifically, methanol, ethanol, bukunol, nonanol, tridecanol, and fuclohexanol. Benzyl alcohol, allyl alcohol, cinnamyl alcohol, furfuryl alcohol, clopargyl alcohol, kera-ol, nerol, ethylene glycol, furopanediol, glycerin, ethanolamine.

Propertool amines, etc. can be mentioned.

Further, alcohol can also be used in the form of its derivatives such as acetals, ketals, and alkyl orthoformates, and VC proceeds in the same manner as in reaction 1.

For example, methyl orthoformate, methyl orthoacetate, 1.1
When -dimethoxycyclohexane or the like is used, dimethyl ester can be obtained in the same manner as when methanol is used.

Pentane, n-hexane as a VC solvent.

Hydrocarbons such as cyclohegizan and heptane can be used, but one of the raw materials is alcohol or its derivative, acecool. Ketals, alkyl orthoformates, etc. can be added to all dicyclopentadiene in an amount greater than theoretically possible, and can also be used as a solvent as is. Also, water * lj'1 = (71,
N,N-dimethylformamide (DMF) is not preferred as a solvent because it lowers the diester yield. to the amount of solvent.

There is no particular limit, but 0 for dicyclopenk diene.
Approximately 1 to 5ffi-'1x5-I'B is preferable.

In addition, in order to remove Li'2, which is produced as a by-product from the solvent during the reaction, the total presence of the base can be removed, and by-products such as halides can be completely suppressed. Sodium, zolopion rib sodium.

Preference is given to salts such as sodium ff16ate. The reaction temperature may be 100'C or higher, although the reaction proceeds near normal temperature.

Special VCf for the pressure of Ippakushika Carbon! Although it is not in ilJ limit,
A pressure of ~5 D KP/cni C is preferred. In the case of low pressure, the reaction time becomes longer and the diester selectivity tends to decrease.

Carbon monoxide does not need to be highly concentrated; oxo gas, which is a mixed gas such as hydrogen, can be used in the same way as carbon monoxide.
It is also industrially advantageous.

Reaction time n, M tAif, , fλ Correlation with carbon pressure accommodation The rate decreases by 1.

Next, a second method will be described in which the diester thus obtained is hydrolyzed and re-esterified.

First, hydrolysis is carried out using a method using hydrochloric acid, chlorinated acid, etc.
Any method using a base such as sodium hydroxide, water, or water (liquid solution) can be used, but in particular, by using a base, the reaction proceeds easily and quantitatively.TricycloC5 , 2,1゜02''6]Des-8-ene-6,4-dicarvone-alkali salt is obtained.Hydrate with base]7U, raw material diester with alcohol solvent such as ethanol or furopanol [bath-scalder, theory Add a slightly excess aqueous alkali solution and stir at around the reflux temperature of the alcohol for 1 to 2 hours (the reaction is easily completed by stirring).

TODC is obtained by treating the alkali salt thus obtained with an acid such as hydrochloric acid or sulfuric acid.

This TODOij is purified by recrystallization using acetonitrile or the like as a solvent to obtain white crystals.

Next, this TCDCV, excessive amount of alcohol and concentrated sulfur ridge 1
~2WJ is added and esterification is carried out while heating and dehydrating under reduced pressure. After the reaction, the desired ester is obtained by completely distilling off the excess alcohol under reduced pressure. The alcohol used in this second method includes, for example, alkyl alcohol, unsaturated alkyl alcohol, and cycloalkyl alcohol.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 (dimethyl ester) Internal volume 100m1! Hastelloy autoclave,
Dicyclopendadiene (D OF D ) 5.951
i' (50 mmoffl), palladium chloride 0.2
67 f <1,5 mm), anhydrous chloride II
(Purity 95゜) 10,4 F (73mmo, (Z),
Pour 24y of methanol and add 651(P) with -carbon oxide.
After pressurizing to /'ctl[), the reaction was started at room temperature (25°C). Immediately – carbon oxide absorption begins 1
After 5 minutes, the pressure reached 9/ctrXC) and absorption stopped. The reaction was exothermic and reached a maximum temperature of 48°C.

After stirring for an additional 15 minutes, the reaction was stopped, the autoclave was returned to room temperature, and carbon monoxide was removed.

Take out the reaction solution and remove the solvent by concentrating the reaction solution as it is.
The Kotoyo product was extracted with n-hexane. As a result of analyzing this n-hexane solution by gas chromatography,
Almost a single peak was detected as the product without any residue in the raw material cyfclopentadiene.

Therefore, this reaction was repeated 5 times in exactly the same way as 1 embroidery of the reaction solution.
After staying overnight, combine 5 doses of n-hexane extract and make J'! ζ
)) 140-145°(,
/0.7 mmHg fraction S5'i/ was obtained.

The analysis results for this distillate were as follows:

11, ((Na, (Jl: z?, so, 176o
, 143o, + 200 (Labour Mu 1)・”'
U-1+MR (CDCi2): 1741.173.
9. i 5 i, 9.131.5.52.5゜51.
5. 46.4.44.5.43.5.4ro1. 41
．． 8.58.7゜ro22(δ)l pヱ・A) -77, Spect "t % (%)) ' 250()
-j, +25), 21 B (I LID).

124 (65), /+6 (80) Elemental analysis showed "+4"+5011 that it was guse-8-ene-3,4-dicarboxylic powdered dimethyl ester (abbreviated as dimethyl ester).

Furthermore, the n-hexane solution was analyzed by gas chromatography.
As a result of quantitative determination, the reaction yield of dinotyl ester was 98 points and 8 points.

Example 2.6 (dimethylnisal) Actual/ffi Table 1 shows the results of a reaction conducted in the same manner as in Example 1 except that part or all of the methanol used in Example 1 was replaced with ortho-1[12-methyl.

Table 1 Examples 4 to 11 (Dimethyl ester) Effects of Example 1 1. and naturalizing agent n'1. Table 2 shows the results of the same reaction except that the molar ratio of catalyst and oxidizing agent and IE4 during the reaction were changed.

Table 2 Rice 1 Reaction Temperature 60°C Half 2 Reaction Temperature 100'C
0KP/cJTiG, therefore the initial reaction pressure 55 k'47
Table 6vc shows the results of carrying out the same procedure as in Example 1, except that the ratio of alcohol and dehydrating agent was changed.

Table 5 *DOPD conversion rate 100% Example 15.16 (Dimethyl ester) Example IVC
Table 4 shows the results of the reaction conducted in the same manner except that the carbon monoxide pressure was changed.

Table 4 *D, OPD conversion rate 100% Actual column 17-20 (Dimethyl ester) actual performance (1)
11/; The reaction was carried out in the same manner as in "1" (1) using a palladium-supported catalyst as the medium, changing the oxidizing agent and the crystallinity for 1 hour, etc. (-J). The results are shown in Figure 5.

Table 5 X M eOH1447+Ii C(OCHb)3
10! /Real h(1ν:1J21(dimethyl ester)
Synchropentadiene (DCPD) 2+29 (t6mo-/) in 2A glass jar 7 Lasco.

Balan chloride l horn, 4.07 (O, D 23 +no
ffl), anhydrous chloride mud 2f1”I (95% purity)
465 g (3.5 moi).

800 methanol was charged, the temperature was raised to 50°C, and then carbon monohexasilide was blown under normal pressure with stirring at a flow rate of 2 n/n for 2 hours.

After the reaction, the reactant was completely cooled, the solvent was removed, and the mixture was extracted with n-hexane. This hexane (135-146°C/'0 by coercive distillation)
Dimethyl ester 284S' (Xlit required 9B) was completely tested at 5mmH7.

Example 22 (di-11-butyl ester) Example 1 ('
In this case, the reaction was carried out in the same manner as in the song 1. except that the methyl alcohol kn-butanol was replaced with 9 and the reaction time was 1.8 hours. two,
Reaction 7 Revised) 1 TJ-C':% 414 After all the solvent was removed by operation, the reaction product 9 was extracted with n-hexane. As a result of gas chromatography analysis of this n-hexane (8 liquid), it was found that 82% of the raw material synchropentadiene (17) remained and 82% of Tonosho (17%) was produced.

This main product was separated and purified from total lJ lamb chromatography Gofufu (/Sukagel Sokogel ((!-200)) Yc,
The results of further analysis were as follows.

Engineering R (Na+;, g): 291] IJ, 1720
．． +180 fL bamboo? , -1, mass spectrum (I
+! 10(chi)l: 554 (20), 261 (
8111゜205 (+003,66(85) Elemental analysis: Drop H26o4 From the above, this main product tgo*Ir'; tricycloCs shown by the formula (6), 2.1.0''・6]Dece8 -ene-5,4-dicarvone ``ζi di-n-butyl ester'' was shown.

Example 23 (Di-n-denle ester) reaction 71M'f
As a result of analysis using a gas chromatograph, unreacted T C
At low D OVi, a single product peak appeared.

The n-decyl alcohol in the reaction mixture was distilled off under reduced pressure in the filtrate 1j/': fZ 1 Chloroform and water were added, and taloloform 1. Separate and dehydrate 1 (4Pt=column chromatography, -(7 licagel Wakogel (c-2on))
The resulting product was purified by Pif6. The analysis results are as follows.

IR (NaCA): 2900.1720.1180
(tv, -1) Mass spectrum (r+7e (%l):
502 (4), 597 (8), 545 (22).

205 (100), 157 (141 Elemental analysis "52) + 5404 From the above, the main products of the nitrate are tricyclo(ri, 2.1.112.6) de-8 shown by the formula 0 to 41. -1
It turned out to be 7-3,4-dicarboxylic acid di-n-decyl ester.

'1 Jha Example 2fy (Diallyl ester) The reaction was carried out in the same manner as in Example Fumi except that allyl alcohol was used instead of alcohol. Also, as a result of post-processing and analysis,
It was confirmed that the main product was produced in Section 64. This main product was separated by column chromatography (silica gel Wakogel (0-200)) and further analyzed, resulting in the following results.

II Wataru Na(1):290[], 1720.1180
(+; m,) Mass spectrum (nH/e (嘱)): 3
02(5), 245(59).

203 (+00), 9B (57) Elemental analysis "+8112201 From the above, this main product is tricyclo[5,2,1,0"I6]dece8-ene-6,
It turned out to be a 4-dicarbonyl diallyl ester.

Example m Example 2f (Synchronohexyl ester) Example edict t
The reaction was carried out in the same manner except that the alcohol was replaced with cyclohexanol and the reaction time was changed to 4 hours. Further, the post-treatment was carried out in the same manner, and as a result of 9 analyses, it was found that the main product was produced in 61 pieces. This main product was separated by column chromatography (Noriiki Gluwakogel (C-200)) and further analyzed, and the results were as follows.

Engineering H(Na(:+4): 2900.1720.11
80 (cm,) Mass spectrum (m/e (%)): 5
86(1), 505(8).

205 (+011), 67 (+9) Elemental analysis:
From the above, this main product is * as C2J(,4C1,
nl'4 formula (trichif o [a 2. denoted by 1'a)
1.02°6]7'-k-8-7-3.4-dicarboxylic acid synchhexyl ester.

Real 7JI! Table 6 shows the results of the same reaction except that the alcohol concentration at 11 Vc and the temperature for 9 hours were changed.

Table 6 Chisen atmosphere'F! J Patent Applicant Applicant San Kagaku Kogyo Co., Ltd. Procedural Amendment (Spontaneous) September 1980 N 1, Indication of the Case 1982 Patent F + Application No. 175075 2, Name of Invention Tricyclo [5, 2, 1 ,02″6]Dece8-en-
44-Dicarboxylic acid diester and its manufacturing method Relationship with the five amendment cases Patent applicant address 6-7-1 Kanda Nishiki-cho, Chiyoda-ku, Tokyo 101
(Ririko telephone number 0474-65-1111) 4 Name of the invention in the application subject to amendment (cocoon, name of the invention in the description 5 Contents of amendment 1) Name of the invention in the application, first part of the description, Name, lines 14-15 from the bottom of page 2, lines 2-4 from the bottom of page 13 [---Tricyclo[5,2,1,02,6] Demo-
8-ene-14-dicarboxylic acid diester---'' is r---)su7riro [5°2, 1.02tsu6]
"Des-5-ene-a9-dicarboxylic acid diester" is corrected.

2) The amended scope of claims is corrected as shown in Attachment 1.

3) Line 3 of page 2 of the specification 4) Delete page 5 of the specification and insert Attachment 2.

5) r---tricyclo[5,2,1,02cylo]dece8-en! on page 10 of the specification, lines 5-5 from the bottom! l,
4-dicarboxylic acid dialkali salt-1-” is replaced with “-”
m-tricyclo[5,2,1,02+' 1teh-3-
x-n-a9-dicarboxylic acid dialkali salt ---'' is corrected.

6) Specification page 10, line 1 7) Specification page 16 Table 3. Example 13. [0u of anti-blocking agent]
Ot---j 2 ``Cuat, correct it as ---J.

8〉Page 19, lines 10-11 of the specification “-11 trisic α[5,2,1,0”]day-8
-ene-5,4-dicarboxylic acid dibutyl ester-
--J to6runok r---tricyclo[5,2,1
,0''']]de-3-ene-a9-dicarboxylic acid di-n-butyl ester.

9) Page 19 of the specification, line 6 from the bottom 10) Page 10 of the specification, lines 4 to 5 from the bottom ,4
-Dicarvone G di-n-decyl ester 111'' was corrected to ``-m-tricyclo[5,2゜1.02.6]dec-3-en-a9-dicarboxylic rff-cy n-tenyl ester'' do.

1 Rimei decoy, page 20 - last line ” I am corrected.

12) Specification, lines 2-3 from the 21st line "---Torijipa [s, 2.1.o2'6] tese-8-en-1
4-dicarboxylic acid sialyl ester---" is replaced with "---tricyclo[5,2,1,02+6]
3-ene-to-9-dicarboxylic acid diallyl ester.''

15) [-m-tricyclo[5,2,1,0'']]de-8-en-5 in the specification, member 22, line 1 14) Bright #l1ls, page 23, lines 1 to 3
4-dicarbonyl cyclohexyl ester---" is replaced by r---tricyclo[5,2,1,0216]
Corrected to ``Dece-3-en-a9-dicarboxylic acid dicyclohexyl ester''.

111,” he corrected.

16) Delete pages 24-25 of the specification and insert Attachment 3.

Attachment 1 Claims (1) Unsaturated alkyl, cycloalkyl k represented by the formula [r] (2) Synchropentadiene, -carbon oxide, alcohol and/or its derivatives An acetal.

A method for producing an 8,9-dicarboxylic acid diester represented by the structural formula [I], which comprises reacting a ketal or an alkyl orthoformate in the presence of a palladium catalyst, a copper or iron compound, and/or oxygen.

Attachment 2 ing.

The compound of the present invention can be produced by two routes represented by the following formula.

Tricyclo[5,2,1,0”6]des-5-ene-8
, 9-dicarboxylic diester (1j each small TODI
IC) (TODB) (Teoc) (TODE) Tricyclo[5,2,1,02''']
': Alkyl different from R, unsaturated alkyl.

Cycloalkyl fund indicated. ) That is, (1) a method using a direct diesterization method of dicyclopentadiene. (2) Diesterification yields 3 Tatsu 6 *+ C, [(,0OONa5.8r (60noM) addition, dicarboxylic anhydrous yield Bsa%

Claims (1)

[Claims] (1) TricycloCs represented by the formula [l], 2.1.02.6] dece-8-ene-3,4-dicarboxylic acid diester (RIts) rugyl, unsaturated alkyl, cycloargyl. ) (2N dicyclopentadiene, - carbon oxide, alcohol and/or its Jb conductor acetal, ketal, orl?', [/alkyl reacted in the presence of a palladium catalyst, a copper or iron compound and/or oxygen) TricycloC5 represented by the formula (I)
,2,1,02.6] Method for producing dece-8-ene-6,4-dicarboxylic acid diester.