JP2713504B2 - Diamino acid derivative - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a diamino acid derivative having a tricyclo ring which has a polyfunctional group and is useful as a raw material for a polymer resin.

BACKGROUND ART A method for producing a monoamino acid derivative having a tricyclo ring by subjecting dicyclopentadiene to an amide carbonylation reaction in the presence of a catalyst comprising rhodium and cobalt is disclosed in JP-A-61-236760. ing. However, in the production method, no reference is made to diamino acid derivatives.

According to the present invention, a diamino acid derivative having a novel tricyclo ring is provided.

Means for Solving the Problems The present invention provides a compound of the formula (I) (In the formula, R ¹ represents a lower alkyl or phenyl, R ²
Represents hydrogen, lower alkyl or benzyl) [hereinafter referred to as compound (I)].
The same applies to compounds of other formula numbers].

In the definition of formula (I), lower alkyl includes straight-chain or branched C1-C4, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

 Next, a method for producing the compound of the present invention will be described.

Compound (Ia) wherein R ² is hydrogen in compound (I)
Is obtained by converting dicyclopentadiene (DCPD) and an amide (II) R ¹ CONH ₂ (II) represented by the following formula (wherein R ¹ has the same meaning as described above) to carbon monoxide, hydrogen and a catalyst. It can be obtained by reacting in the presence.

Compound (II) is generally used in a range of 0.5 to 10 mol, preferably 1 to 4 mol, per 1 mol of DCPD.

As for the gas mixture ratio of carbon monoxide and hydrogen, carbon monoxide is usually used in a range of 0.1 to 10 mol, preferably 0.2 to 10 mol, per mol of hydrogen.

As a catalyst, dicobalt octacarbonyl [Co ₂ (C
O) ₈ ] alone or as a complex with iron carbonyl, ruthenium carbonyl, nickel carbonyl, palladium carbonyl and the like.

The amount of the catalyst used is not particularly limited, but is usually used in the range of 0.01 to 100 gram atoms as cobalt metal with respect to 100 moles of DCPD, and preferably in the range of 0.05 to 6 gram atoms. In the case of a composite system, the other metal is used in the range of 0.01 to 100 mol per 1 mol of the cobalt metal.

In order to stabilize the catalyst, for example, a phosphine compound such as trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, and 1,2-bis (diphenylphosphino) ethane can be used.

The reaction proceeds without solvent, but a solvent can also be used. As the solvent, a solvent for dissolving DCPD is preferable, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, esters such as methyl acetate and ethyl acetate, ketones such as acetone and methyl ethyl ketone, benzene, toluene and xylene And aromatic hydrocarbons such as hexane and heptane.

This reaction is carried out under pressure, and the reaction pressure is 10
400400 kg / cm ² , preferably 70-300 kg / cm ² , the reaction temperature is 20-250 ° C., preferably 60-170 ° C., and the reaction time is 5 minutes to 20 hours.

Compound (I) can be similarly obtained by using compound (III) represented by the following formula instead of DCPD as a starting compound.

Compound (III) can be prepared by a known method [New Synthesis w.
ith Carbon Monoxide, Berlin-Heidelberg-New York: S
pringer-Verlag P100-105 (1980)].

Compound (Ib) in which R ² is lower alkyl or benzyl in compound (I) can be obtained by esterifying compound (Ia). Examples of the esterification method include a method using diazoalkanes such as diazomethane and diazoethane, and a method of reacting with corresponding alcohols in the presence of a catalyst.

The starting compound (Ia) can be subjected to an esterification reaction without isolation and purification. Further, in the production method of the above (Ia), as a reaction solvent, for example, methanol,
By using aliphatic alcohols such as ethanol and isopropanol or alcohols such as benzyl alcohol, esters (Ib) which correspond at a stroke to DCPD
You can also get

The target compound in the above production method is isolated by subjecting to a purification method commonly used in organic synthetic chemistry, for example, filtration, extraction, washing, drying, concentration, recrystallization, various chromatography, etc.
It can be purified.

Since the compound obtained by the present invention has a tricyclo ring provided with a polyfunctional group, it is useful as a raw material for a hard and strong high-functional polymer resin, or as a raw material for a special chelating agent or surfactant. It is also expected as a physiologically active substance such as an antiviral agent.

Hereinafter, embodiments of the present invention will be described with reference to Examples and Reference Examples.

Example 1 In a 500 ml electromagnetic rotating autoclave, 39.7 g (0.3 mol) of DCPD, 35.4 g (0.6 mol) of acetamide, 2.1 g (2 mol%) of dicobalt octacarbonyl and 1,4-dioxane 3
The autoclave charged with 00 g was replaced with a mixed gas of carbon monoxide and hydrogen (1: 1.3 mol) and reacted at 130 ° C. for 5 hours at a pressure of 180 kg / cm ² . After cooling, 396.3 g of reaction product was obtained. Gas chromatography (GLC) (Column: Silicon SE-30 3φ × 3m; Temperature condition: 60 → 290 ℃, 10 ℃)
/ Minute heating; detector: FID), the conversion rate of DCPD is
100%.

By treating 100 g of the reaction product with diazomethane, 96.6 g of a product (production yield by GLC: 25%) was obtained. 50 g of this was taken and subjected to silica gel column chromatography (eluent; methanol: ethyl acetate = 5: 95),
2 g of compound A (purity by GLC: 67%; total yield: 9%) was obtained as white needles.

 Compound A showed three peaks as a result of GLC analysis.

Retention time (min) production rate (%) Peak I (Compound A ₁₎ 34-35 18 Peak II (Compound A ₂₎ 35-36 24 Peak III (Compound _{A 3) 36~37 25 GC-MS} (m / z ): 394 (M ⁺ ) Elemental analysis (%): Calculated for C H N as C ₂₀ H ₃₀ N ₂ O ₆ (molecular weight 394.47); 60.90, 7.67, 7.10 found; 1) 61.02, 8.08, 6.78 2) 60.84 , 7.91, 6.84 IR (KBr) cm ^-1 : 1733, 1643, 1538 From the above results, it was confirmed that Compound A had the following structural formula.

Next, 1 g of the compound A was taken, diluted with 5 g of methanol-water (3: 2), and then subjected to liquid chromatography (column: inertosyl Prep-ODS 20.0 × 250 mm; eluent: methanol: water = 1: 1).
1; elution rate: 5 ml / min; Detector: RI) and the Compound A ₃ isolated using. The compound was subjected to GLC (capillary column: CP-Sil
-5CB50cm × 0.25mm; temperature condition 270 → 290 ℃, 1 ℃ / min;
Detector: FID) showed a single peak.

^{IR (KBr) cm -1: 3270,1743,1655,1541} 13 C-NMR (CDCl 3) δ (ppm): 22.8,23.8,27.5,34.5,3
7.0,40.2,42.2,42.3 × 2,46.4,49.1,52.2,55.8,56.0,17
0.3,174.3 ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.25 and 1.53 (4H), 1.
50 and 1.63 (2H), 1.62 and 1.72 (2H), 1.84 (1
H), 1.9 to 2.05 (8H), 2.13 (2H), 2.50 (1H), 3.73 (6
H), 4.28 (1H), 4.47 (1H), 7.0 the above results, Compound A ₃ is to show the following structural formula was confirmed.

Example 2 A 50 ml electromagnetic rotating autoclave was charged with 2 g (15 mmol) of DCPD, 1.77 g (30 mmol) of acetamide, 0.2 g (4 mol%) of dicobalt octacarbonyl and 30 ml of 1,4-dioxane. The autoclave was replaced with a mixed gas of carbon monoxide and hydrogen (1: 1.3 mol) and reacted at 130 ° C. for 6 hours at a pressure of 150 kg / cm ² .

As a result of the same GLC analysis as in Example 1, the conversion rate of DCPD was 100%.
And 25% yield of compound A by diazomethane treatment
(Compound A ₁ 5%; A ₂ 8%; A ₃ 12%).

Example 3 In a 50 ml electromagnetic rotating autoclave, 2 g (15 mmol) of DCPD, 1.77 g (30 mmol) of acetamide, 0.1 g (2 mol%) of dicobalt octacarbonyl and 30 ml of methanol
ml. The autoclave was replaced with a mixed gas of carbon monoxide and hydrogen (1: 1.3 mol), and at a pressure of 150 kg / cm ² ,
The reaction was performed at 150 ° C. for 1 hour.

As a result of the same GLC analysis as in Example 1, the conversion rate of DCPD was 100%.
And the production yield of compound A 2% (compound A ₂ 1%; A ₃₁
%)Met.

Example 4 DCPD (15 mmol), acetamide 1.77 g (30 mmol), dicobalt octacarbonyl 0.1 g (2 mol%), methanol 3.5 g were placed in a 50 ml electromagnetic rotating autoclave.
(109 mmol) and 30 ml of 1,4-dioxane. The autoclave is charged with a mixed gas of carbon monoxide and hydrogen (1:
(1.3 mol) and reacted at 130 ° C. for 4 hours at a pressure of 150 kg / cm ² .

As a result of the same GLC analysis as in Example 1, the conversion rate of DCPD was 100%.
And production yield 8% Compound A (Compound A ₂ 4%; A ₃ 4
%)Met.

Reference Example 1 DCPD 6.6 g (50 mmol), acetamide 6.0 g (102 mmol), dicobalt octacarbonyl 0.68 g (4 mol%), hydride carbonyl tris (triphenylphosphine) rhodium (I) 0.092 in a 100 ml electromagnetic rotating autoclave. g (0.2 mol%) and 1,4-dioxane 30 g
Was charged. The autoclave was replaced with a mixed gas of carbon monoxide and hydrogen (1: 1.3 mol), and the pressure was reduced to 100 kg at a pressure of 140 kg / cm ^2.
The reaction was carried out at 2 ° C. for 2 hours.

As a result of the same GLC analysis as in Example 1, the conversion rate of DCPD was 100%.
Met.

Next, when the product was treated with diazomethane, the monoamino acid methyl ester derivative was analyzed by GLC (retention time 2
(3 to 24 minutes), 81% formation was observed, but no formation of compound A was observed.

Reference Example 2 DCPD 6.6 g (50 mmol) acetamide 6.0 g (102 mmol), dicobalt octacarbonyl 0.68 g (4 mol%), hydride carbonyl tris (triphenylphosphine) rhodium (I) in a 100 ml electromagnetic stirring type autoclave.
0.092 g (0.2 mol%) and 30 g of 1,4-dioxane were charged. The autoclave was replaced with a mixed gas of carbon monoxide and hydrogen (1: 1.3 mol), and at a pressure of 150 kg / cm ² , 130 ° C
For 2 hours.

As a result of the same GLC analysis as in Example 1, the conversion rate of DCPD was 100%.
And the yield of the monoamino acid methyl ester derivative by treatment with diazomethane was 13%, but the formation of compound A was not observed.

Claims (1)

(57) [Claims] (1) (In the formula, R ¹ represents a lower alkyl or phenyl, R ²
Represents hydrogen, lower alkyl or benzyl).