JPS62226934A - Norbornene derivative - Google Patents

Abstract

NEW MATERIAL:A norbornene derivative of formula I (R1 is vinyl, ethylidene or ethyl; R2 and R3 are hydroxyl, alkoxy, hydroxymethyl, alkoxymethyl, acyl, etc.; one of R2 and R3 is H or alkyl; the group of formula II is single or double bond). EXAMPLE:6-Vinyl-2-norbornylmethylidenemalonic acid diethyl ester. USE:Useful as a perfume, plasticizer, crosslinking agent, reactive diluent, biochemical drug, etc. Also useful as a basic raw material for the synthesis of other norbornene compounds. PREPARATION:The compound of formula III (R4 is H, alkyl or acyl) which is one of the compound of formula I can be produced e.g. according to the reaction formula by Wittig reaction using LiAlH4, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is a powerful basic technology for synthesizing other norbornene compounds using vinylnorbornene, ethylidenenorbornene, or ethylnorbornene obtained in the petrochemical industry as a raw material. In addition to being moisturizing, this product also contains fragrances and plasticizers.

It has a wide range of industrial applications as a crosslinking agent 1-reactive diluent, biochemical drug, etc.

[Prior Art], [Problems to be Solved by the Invention] Utilizing the selective reactivity of the endocyclic double bond in vinylnorbornene, ethylidenenorbornene, or ethylnorbornene, norbornane or A technique for synthesizing analogous compounds thereof and attempting to obtain the product of the present invention, which is a more effective synthetic intermediate, is conventionally known, and no such product exists. As a result of many years of research and efforts, the present inventors have now succeeded in developing the novel norbornene derivative referred to in the present invention.

[Means for Solving the Problems], [Operation] The present invention relates to a novel norbornene derivative represented by the following general formula (1).

However, in formula <1), the ratio represents either a vinyl group, an ethylidene group, or an ethyl group, and R2 and R1 are a hydroxyl group, an alkoxy group, a hydroxymethyl group, an alkoxymethyl group, an acyl group, an acyloxy group, a carboxyl group, and a carbalkoxy group. is at least one atomic group selected from the group consisting of a group consisting of a group, an acyloxymethyl group, a cyan group, and a carboamino group, and any one of & and R3 may be a hydrogen atom or an alkyl group; It represents a single bond or a double bond.

Particularly important among the compounds represented by formula (1) are novel norbornene derivatives represented by formulas CI[) to (Wataru) shown below. However, in 2〇D~(XI), R
4゜陀 means a hydrogen atom or an alkyl group, (I>
.

In the case of formulas (I) and (■), an acyl group is also added, and ('
) also represents a hydroxyl group, which may be the same or different, and n represents an integer of 0 or 1.

Although there are several methods for synthesizing the novel norbornene derivatives of the present invention, one representative method is shown by the above formula (
The following examples will be applied to the additional compounds of 1) to 1).

This method using the Witschitsch reaction is convenient in that most things can be synthesized in terms of real limbs.

There are constraints in terms of raw materials, and the drawback is that it is not cheap.

This method corresponds to a Grignard-type, Wurz-type, or Ullmann-type reaction, and the yield varies depending on the structure of the raw materials, and there are generally many types of by-products.
It is an inexpensive method for the synthesis of certain compounds.

Although this aldol condensation reaction has the drawback of producing self-condensates and other by-products depending on the raw materials, it can be widely carried out industrially if the conditions are set.

In reactions involving this erulate anion, hydrogen denomination and hydrogen halogenation occur actively due to the structure of the L halide, and the yield is sometimes poor. Generally (lO) secondary halide) CHBr and also primary halide -C
The yield is better when H2Br type raw materials are used.

Methods using this condensation reaction of active methylene compounds (Knoeffenagel reaction, etc.) generally have good yields and are convenient for synthesizing many of the compounds of the present invention. As an active methylene compound, R4COCH2C0RB (D Ho7% W
a 7 Acid varnish f A/ R40COCH2COOR
5.

Malononitrile CH2(ON)2, acetic acid ester/I/CH3COCH2COOR4, etc. are used.

Compounds obtained using the above reactions such as ■ to ■ are as shown in It becomes an alcoholic compound as shown in the present invention, which can be further derived into an alkoxy compound or an ester compound by alkylation or acylation, and from which the side chain can be extended. .

The method will be detailed in the examples.

The inventors of the present invention have conducted numerous experiments to clarify the superiority of the present invention, but in order to further explain the technical content of the present invention, we have selected representative examples from among the numerous experimental examples. This will be shown below as an example.

〔Example〕

Example 1 0.10 mol of 5- or 6-piny-2-norbornanecarbaldehyde and 10.12 mol of diethyl malonate/L.

1 ml of piperidine. Acetic acid 2 resistance and toluene 300g/
After boiling and removing the water produced as an azeotrope 9
When the reaction mixture is distilled under reduced pressure, 5- or 6-pini/v-
2-Norbornyl methylitene malonic acid diethyl/l/(b
p, 130° C./0.5 ffHI) in a yield of 65 cm. The analysis results are as follows.

i (liquid film), (n-1) i 3060.293
5.2870.1720°1650, 1180°"Hrml: (CC114)i δ6.75~6.60
(d, IH), 6.15-5.60 (m, IH),
5.20~4.75 (m, 2H), 3.85~
3.65 (q, 4H), 2.50~t10 (m, 16H
).

Elemental analysis value Straw C = 69. s achi, H=8.30
%,(Calculated value.

C17H2404,! : Shite, C=69.83%,
H=8.2796).

Examples 2 to 3 When the same procedure as in Example 1 was carried out except that 5- or 6-piny-2-norbornanecarbaldehyde was replaced with the aldehyde shown in the following table, the results shown in the following table were obtained.

Examples 4 to 6 0.05 mol of the products obtained in Examples 1 to 3 (raw materials in the following table) was dissolved in 100 g/Ki of ethanol, and 5 y of sodium borohydride was added thereto for 1 hour under water cooling. After the reaction, the reaction mixture was poured into dihydrochloric acid solution and extracted with benzene. The benzene extract was separated, dried over anhydrous sodium sulfate, and then distilled to obtain the results shown in the following table.

Examples 7-9 The products obtained in Examples 4-B (raw materials in the following table) 0.02 mo/
It was dissolved in 150IIll of I/ft ether/l, 3 moles of lithium aluminum hydride was added thereto, and the mixture was reacted for 2 hours at room temperature, diluted with ethyl acetate, left overnight, and then poured into an aqueous solution of hydrochloric acid for 5 liters of benzene. Extract.

When the benzene extract was separated, dried over anhydrous sodium sulfate, and then distilled, the results shown in the following table were obtained.

Examples 10 to 12 0.01 mol of the products obtained in Examples 7 to 9 (raw materials in the following table) were mixed with 60 g of pyridine and 30 m of acetic anhydride. After the mixture was fermented and reacted at 50°C for 5 hours, the 9 reaction mixtures were poured into cold water and operated in the same manner as in Examples 4 to 6. The results are shown in the following table.

Example 13 The 5-mer was 1.0 mol of 6-pinyl-2-norbornanecarbaldehyde and 1.1 mol of ethyl acetoacetate/L'.

3 ml piperidine + 6xl acetic acid and 11 ml benzene
(7) When the mixture is operated in the same manner as in Example 1, 2-(
Ethyl 5- or 6-pinyl-2-norbornyl) methylideneacetoacetate (bp, 125°C/611#Hf)
was obtained with a yield of 80%. The analysis results are as follows.

i, r (liquid film), (cII-”); 3050.2
920.2870.1690°1660, 1640.1
150゜1 shame (C (J4); δ6.80~6.78 (d,
IH), 6.15-5.70 (m, IH), 5.
15-4.70 (m, 2H), 3.30-3.20
(q, 2H), 2.20(s, 3H), 2.5
0-0.95 (m, 1! IH).

Elemental analysis value; C=73.09%, H=8.60%,
(Calculated value.

016, H2203 as C=73.25%, H=8
．． 45%).

Examples 14 to 21 Examples were carried out using the aldehydes shown in the following table in place of 5-or 6-piny-2-norbornanecarbaldehyde in Example 13, and the active methylene compounds shown in the following table in place of ethyl acetate. When operated under the same conditions as No. 13, the results shown in the following table were obtained.

The compounds in the above table can be converted into saturated bonds by reducing the newly formed double bonds with sodium borohydride using the methods of Examples 4 to B.

The diester bond can then be reduced to the alcohol with lithium aluminum hydride using the methods of Examples 7-9. In addition, Examples 15, 16, and 18 in the above table.
19.21 and its reduced product are converted to C00 by hydrolysis.
It is also easy to change each of CHs, COOC2H5 and ON to a COOH group. Those containing ON groups can also be reduced to CH2NH2 groups by using H2/Raney nickel or H2/white kA catalysts.
It is also easy to convert it into a CONH2 group by partial hydrolysis.

Example 22 Sodium hydride 3.2 g, diethyl ethoxycarbonylmethylsulfonate IL/376F, benzene 40 tpt
5- or 6-vinylnorbornanone in a mixture of 20
After adding 1 and reacting for 3 hours at room temperature to 60°C, the benzene layer was separated and distilled to obtain 2-(carboethoxymethylidene)-5- or 6-vinylnorbornane (1).
p, 110°C/4ffHf) with a yield of 70%. 4.09f of this product was dissolved in 50 ml of tetrahydrofuran, 0.36f of lithium aluminum hydride was added, and the reaction mixture was allowed to react overnight while cooling with water.The reaction mixture was then poured into dilute sulfuric acid, extracted with ether, and the extract was anhydrous. Distillation with sodium sulfate gives 2-(2-hydroxyethylidene)-5-or-vinylnorbornane (bp, 88°C).
/2 whale Hp) with a yield of 48%. The analysis results are as follows.

j-r (liquid film), (ffl-”) i 3360.3
060.2930.2870゜1645, 1100゜"Hnmr(CDC"); δ6.15~5.30(m
, 2H), 5.20-4.60 (m, 2H), 3.
95-3.80 (d, 2H), '1.55-3.30
(t, IH), 2.60-1.10 (m, 9H).

Elemental analysis value, C=80.61%, H=9.87%, (
Calculated value.

As CnHxsO, C=80.44%, H=9.83).

Example 26 20f of 2-(carboethoxymethylidene)-5- or 6-pinylnorpornan obtained in Example 22, 300 ml of ethanol-1v? , 5 Typandium carbon catalyst 1.
When 5-norborni is placed in a pressure cooker and hydrogenated at a hydrogen pressure of 3.5 kq/cd (5- or 6-ethyl/L'-2-norborni/) acetic acid: '-f/l' (bp, 91-93
℃/2.0m*Hf) with a yield of 80%, and when this is hydrolyzed with an aqueous alkali solution, 2-(5- or 6-ethyl/l/-2-norbornyl)ethano-#(bp, 83
°C/1.5 fin HfI) with a yield of 90 cm. The analysis results are as follows.

ir (liquid film), Can); 3400.2925
．． 2870.1100゜"Hnmr, (CDOIIs
); δ3.60-3.50 (t, 2H), 3.
40-3.30 (t, 1H), 2.55-1.1
0 (m, 17H).

Elemental analysis value; C=78.65%, H=12.08%
, (Total! ([.

As C11H200, C=78.51%, H=11.
98chi).

Example 24 If the same procedure is performed using 5- or 6-vinylnorbornanecarbaldehyde in place of 5- or 6-vinylnorbornanone in Example 22, 3-(5- or 6-piny-2-norbornyl) is obtained. Ethyl acrylate (bp, 99
°C/1.0% Hy) with a yield of 86%. This product was reduced with palladium hydrogen in the same manner as in Example 23 to form 3-(5- or d6-biniA/-2-norbornyl).
Ethyl propionate (bp, 92 /1.0ffHf
) is obtained in a yield of 79-. When this product is reduced with hydrogen by a conventional method using Raney nickel as a catalyst, 3-(5-
'l' or 6-ethyl-2-/N) -1-f
Donkey/-N (1)p, 100'0/2. OmHl
) with a yield of 90%. The analysis results are as follows.

ir (liquid film), (3-”month 3450.2935.28
70.1100゜”Hnmr (CD0A'3) i
δ3.75~3.60 (t, 2H), 3.40~
3.30 (t, IH), 2.60-1.05 (m, 19
H).

Elemental analysis value i C=79.20chi, H=12.03%
, C calculated value.

Cl2H220 and LteC=79.06%, H=12.
16%).

Example 25 When 5- or 6-ethylidene-2-norbornanecarbaldehyde was used in place of 5- or 6-vinylnorbornanone in Example 22, the same procedure was performed to obtain 3-(5- or 6-ethylidene-2 -Norbornyl) ethyl acrylate (bp, i1o°C/0.7 fiHy) with a yield of 96 tons. The analysis results are as follows.

j-r (liquid film), (al-”); 3070.2
930.2875.1720°1665, 1180°"Hnl['(C(J4)iδ6.80~6.70 (
4 d, IH).

5.60-5.50 (2 pieces (1, IH), 5.5
0-5.05 (m, IH).

3.65-3.55 (t, 2H), 2.50-1
．． 10 (m, 15H).

Elemental analysis value i C=76.43chi, H=9.20 (calculated value.

As 014H2002, C=76.32%, H=9.1
5%).

〔Effect of the invention〕

The completion of the present invention will enable significant development of chemical processing methods for norbornene materials obtained in the petrochemical industry, and its contribution to industry will be enormous.

Claims (11)

[Claims] (1) A norbornene derivative represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) However, in formula (I), R_1 represents either a vinyl group, an ethylidene group, or an ethyl group, and R_2, R_
3 is at least one atom selected from the group consisting of a hydroxyl group, an alkoxy group, a hydroxymethyl group, an alkoxymethyl group, an acyl group, an acyloxy group, a carboxyl group, a carbalkoxy group, an acyloxymethyl group, a cyan group, and a carboamino group. In addition, either one of R_2 and R_3 may be a hydrogen atom or an alkyl group, and ■ represents a single bond or a double bond. (2), the formula (I) is represented by the following general formula (II
) The norbornene derivative according to claim 1, which is represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) However, in formula (II), R_4 represents a hydrogen atom, an alkyl group, or an acyl group. (3), the formula (I) is represented by the following general formula (II
The norbornene derivative according to claim 1, represented by I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) However, in formula (III), R_4 represents a hydrogen atom, an alkyl group, or an acyl group. (4), the formula (I) is represented by the following general formula (IV
) The norbornene derivative according to claim 1, which is represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) However, in formula (IV), R_4 represents a hydrogen atom or an alkyl group. (5), the formula (I) is represented by the following general formula (V
) The norbornene derivative according to claim 1, which is represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) However, in formula (V), R_4 represents a hydrogen atom or an alkyl group. (6), the formula (I) is expressed by the following general formula (VI
) The norbornene derivative according to claim 1, which is represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) However, in formula (VI), R_4 and R_5 represent a hydrogen atom, an alkyl group, or an acyl group, and these may be the same or different. (7), the formula (I) is expressed by the following general formula (VI
The norbornene derivative according to claim 1, represented by I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) However, in formula (VII), R_4 and R_5 represent a hydrogen atom or an alkyl group, and these may be the same or different. (8), the formula (I) is expressed by the following general formula (VI
The norbornene derivative according to claim 1, which is represented by II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VIII) However, in formula (VIII), R_4 and R_5 represent a hydrogen atom or an alkyl group, and these may be the same or different. (9), the formula (I) is expressed by the following general formula (IX
) The norbornene derivative according to claim 1, which is represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IX) However, in formula (IX), R_4 and R_5 represent a hydrogen atom, a hydroxyl group, or an alkyl group, and these may be the same or different. (10), the formula (I) is represented by the following general formula (
The norbornene derivative according to claim 1, represented by X). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (X) However, in formula (X), R_4 and R_5 represent a hydrogen atom or an alkyl group, and these may be the same or different, and n is an integer of 0 or 1. (11), the formula (I) is represented by the following general formula (
The norbornene derivative according to claim 1, which is represented by X I ). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(X I)