JPS62226949A - Nitrogen-containing norbornene derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (the bond containing dotted line is single or double bond; R1 is methyl, ethyl or vinyl; when R2 is H, R3 is (substituted) hydrocarbon group; when both R2 and R3 are hydrocarbon groups, terminals of said hydrocarbon groups may be bonded with methylene, methine, carbonyl or O to form a cyclic group; n is 0 or 1; when N is bonded through double bond, R2 is absent). EXAMPLE:(6-Vinyl-2-norbornyl)methylidene-O-carboethoxyaniline. USE:Perfume, plasticizer, crosslinking agent, rust-proofing agent, antioxidant or intermediate for organic syntheses. PREPARATION:The compound of formula I can be produced by reacting a norbornanone of formula II or norbornyl aldehyde of formula III with an amine in the presence of a mild acidic catalyst (e.g. sulfamic acid).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to nitrogen-containing norbornene derivatives, and the compounds shown in the present invention can be used as fragrances, plasticizers, crosslinking agents,
It has a wide range of applications in various industries as a rust preventive, antioxidant, or organic synthesis intermediate.

[Prior art], [Problems to be solved by the invention] Until now, a large number of compounds having the structure of a thick base have been synthesized mainly in the fragrance industry, but they have little change in fragrance tone and The compound was extremely unsuitable for use in applications other than perfumery.

As a result of many years of research and effort, the inventors of the present invention have completed a completely novel invention.

[Means for solving the problem] [Operation] The present invention relates to a nitrogen-containing norbornene derivative represented by the following general formula (1).

However, in formula (1), =π represents a single bond or a double bond, R represents a methyl group, an ethyl group, or a vinyl group, and when R2 is a hydrogen atom, R3 is a hydrocarbon group or a substituted Represents any hydrocarbon group, R
When both 2 and R3 are hydrocarbon groups, the terminal of the hydrocarbon group may be bonded to a methylene group, a methine group, a carbonyl group, or an oxygen atom to form one cyclic group, and n is 0 or 1 and ``When N = N, +
R2) indicates that it does not exist. Among the derivatives represented by formula (1), when R2 is a hydrogen atom, R3
Of particular interest will be compounds in which R is a phenyl group with an 0-alkoxycarbonyl group, and compounds in which R2 and R3 are tetramethylene, pentamethylene or oxybis(dimethylene) groups.

Now, the nitrogen-containing derivatives represented by formula (1) can be broadly classified into norbornanone derivatives (1) and norbornylaldehyde derivatives (1) and (2), but all of them include important compounds. are doing.

The present inventors have found that norbornanone shown in the following formula (4),
As a result of numerous reactions of norbornyl aldehyde shown in formula (2) with various amines, etc. in the presence of a catalyst or a third substance, R1 or R1 as a substituent of norbornanone was As long as raw materials having a dimethyl group, ethyl group or vinyl group are used, under the reaction conditions described in the present invention, (■) to (W) can be obtained without producing any other by-products due to unknown reactions. It was discovered that the nitrogen-containing norbornene derivative shown in the figure can be obtained in good yield.

Here, the relationships from equations (tl and (to)) to equations (1) to (W) are briefly illustrated as shown below.

(1) Reactions in the above diagram are carried out using mild acidic catalysts such as sulfamic acid, phosphoric acid, boron fluoride complex salts, solid acids (such as silica gel), acidic ion exchange resins, and the presence of organic carboxylic acids or organic sulfonic acids. It has been found that the presence of strong acids and strong alkaline substances is particularly undesirable because it promotes rearrangement and decomposition of reactants. Since the reaction shown in the above diagram proceeds from the left side to the right side due to dehydration, it is recommended that water be removed from the reaction system by an appropriate method, such as distillation of an azeotrope.

In the above diagram, when trying to obtain formula (1) or (V), it is generally preferable to use a large excess of amine or amide and formic acid as well as raw material ketone or aldehyde in order to prevent side reactions. It is best to use 3 to 6 times the mole amount. In order to obtain the formula (1) or (V), it may be advantageous to perform the reduction separately as shown in the figure, without relying on such a step, for example under controlled conditions using sodium borohydride etc. When reduced with , the target product can be derived with good yield. Next, specific examples of amines that are raw materials for the present invention (including amines constituting acid amide) include aliphatic primary amines, aliphatic secondary amines, cycloalkylamines, aniline, and nuclear substitution. Foreign cyclic amines, etc., including anisotropic substances, etc., and 0 if intended as fragrance substances.
-Aminobenzoic acid ester and N-methyl-〇-amine benzoic acid ester are conveniently used, and the reaction products are both pleasant aroma substances with a sweet floral aroma with a woody tone, and both are liquid. Therefore, it is very easy to use when preparing fragrances.

The present inventors have conducted numerous experiments regarding the above-mentioned present invention, and have clarified the superiority of the present invention. Some experimental examples will be extracted and shown below as examples.

〔Example〕

Example 1. 5-2* is 6-vinylnorbornane carbaldehyde 0.
A mixture of 1 mol, 0.1 mol of ethyl 0-aminobenzoate, 0.6 g of benzenesulfonic acid and 500 πl of benzene is boiled for 6 hours. During this time, water is generated as the reaction progresses, and this is removed by distillation as an azeotrope with benzene. After water no longer distills out, the reaction mixture is cooled and then poured into cold water. . This water mixture is extracted with ether, the ether extract is dried over anhydrous sodium carbonate, and the ether is distilled off.
-Pinyl-2-norbornyl) methylitene-〇-carboethoxyaniline crude product is obtained, and when this is purified by redistillation method or column chromatography method, the pure product becomes a pale yellow transparent fluid liquid (bp 161-163℃/o,
2tttmmq). Yield is 92
Indicate the next analysis value.

ir (liquid film), (CII!') i 3050.29
25.2870.1720゜1670.1650.12
0n.

'Hnmr (CDCIJ 3) i J" 7.8
0-7, 55 (m, 4H), 6.25-6.15
(m11H), 3.8 [] ~ 3.65 (q, 2H)
, 2.50-1.00 (m, 12H).

Elemental analysis value 1c = 75.80%, H = = 7.09%, N
=5.27%.

(Calculated value, 017H1902N, Toshite c=75.81
%, H=7.11%.

N = 5.20%).

Examples 2 to 15 In Example I, the carbonyl compounds shown in the following table were used for the 5-strapping 6-vinylnorbornanecarbaldehyde, and the amines shown in the following table were used for the ethyl 0-aminobenzoate. When the same operation as in Example 1 was performed, the results were as shown in the following table.

Example 16゜(5-1 or 6-pinyl-2-norbornyl)methylidene-〇-triboethoxyaniline 1 obtained in Example 1
0 f was dissolved in 1 oomt of ethanol, 1 g of sodium borohydride was added thereto, stirred and kept at 50'C for 1 to 2 hours, then the reaction mixture was poured into cold water and extracted with ether to obtain an ether extract. After separating it and drying it with anhydrous magnesium sulfate, it is distilled! = (5-t7'c#-
Ethyl 6-pinyl-2-norbornyl) methylanthranilate (bp, 170-171"C/0.25 Hf) 9 f was obtained. The analysis results were as follows.

j-r (liquid film), (CM) i 3350.3050.
2930.2875.1690.1180°1Hnmr (ODO43); J 7.90-7.65
(m, iH), 7.35-6.95, (m, iH)
, 6.65-6.35 (m, 2H), 5.90-5.
45 (8, IH), 6.05-5.40 (m, IH)
, 5.14-4.65 (m.

2H), 4.45-4.10 (Q, 2H), 2.80
~4.00 (m, 12H), 1.50~1.25 (t
, 511).

Elemental analysis value i C= 76.20chi, I(= 8.44
%, N=4.70%, (calculated value, C19H2602N1
As O = 76.22 cracks, H = 8.42%, N = 4.
68%).

Example 17. ~26゜If the procedure in Example 16 is repeated using the thick base shown in the following table in place of (5-or-vinyl-2-norbornyl)methylidene-〇-carboethoxyaniline, the results shown in the following table will be obtained. It will be done.

Example 27 A mixture of 0.1 mol of 5-996-piny-2-norbornanecarbaldehyde, 0.12 mol of morpholine, 1 mol of p-chlorobenzenesulfonic acid and 500 πt of benzene was boiled to cause water to azeotrope with the benzene. The reaction is allowed to continue until no distillation occurs. After cooling, the reaction mixture is poured into cold water, extracted with ether, and the extract is dried over anhydrous sodium carbonate and distilled to give 2-(morpholinomethylidene)-5- or 6.
-vinylnorbornane ('bp, 125''C/211
! rHg) with a yield of 70%. The analysis results were as follows.

1r (liquid film) (CM-”); 3090.293
0.2875.1660゜'Hnmr(CDCl2);
6.15-5.50 (m, 2H), 5.20-4
．． 55 (m, 2H), 3.70~5.5s (t, ,
4H), 3.40-5.20 (t, 4H), 2.80-
1.15 (m, 9H).

Elemental analysis value jc = 76.52%, H = 9.62chi, N
= 6.41%, (calculated value, C14H210, C as N1! = 76.66%, H = 9.65chi, N = 6
．． 39%).

Examples 28-31゜Same procedure as in Example 27, using aldehydes shown in the following table instead of 5-i or 6-piny-2-norbornanecarbaldehyde, and using amines shown in the following table in place of morpholine. do. The results shown in the table below were obtained.

(Example 1'i 32゜5- or 6-pinyl-2-norbornancarp 0.1 mol, 19-formylmorpholine a, Brahma 2
and 0.4 moles of 85% formic acid are placed in a flask with a counterflow condenser and the flask is placed on an oil bath at 150''C.

After reacting for about 7 hours, the counterflow condenser was replaced with a distillation tube to distill off formic acid together with water. The reaction mixture was poured into a 10% aqueous sulfuric acid solution, and after steam distillation, the distillation residue was made alkaline with sodium hydroxide and extracted with ether. When the ether extract is dried over anhydrous potassium carbonate and distilled, 2-(morpholinomethyl)-5- or -vinylnorbornane (
bp, 110″c/1tttyHq) with a yield of 62%.
This is the same compound that was slowly hydrogenated using a Raney nickel catalyst under normal pressure. The analysis results are as follows.

Elemental analysis value, C = 75.92, H = 10.51, N
6.29 chi, (calculated value, C,, H230, N, C = 75.97 chi, H = 10.47) Hiroshi N = 6.33 chi).

〔Effect of the invention〕

Includes thick bases, tertiary amines, and tertiary amines containing a lunene ring or vinylnorbornene ring as a structural part, as well as secondary amines and tertiary amines containing the above-mentioned ring structure and methylidene group. The products of the present invention have a wide range of uses as fragrances, plasticizers, crosslinking agents, epoxy resin curing agents, curing aids for urethane composite resins, rust preventives, antioxidants, and synthetic intermediates. . Therefore, it can be said that the industrial value of the present invention is enormous.

Claims (1)

[Claims] (1) A nitrogen-containing norbornene derivative represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, in formula (I), ■ represents a single bond or double bond, R_1 represents a methyl group, ethyl group, or vinyl group, and R_2 represents hydrogen. When an atom, R
_3 represents either a hydrocarbon group or a substituted hydrocarbon group, and when R_2 and R_3 are both hydrocarbon groups, the terminal of the hydrocarbon group is bonded to a methylene group, a methine group, a carbonyl group, or an oxygen atom to form a monomer. In addition, n represents 0 or 1, and when N is =N, it means that -(R_2) does not exist.