JPS624266A - Novel 4-pyridyl-4-cyanopimelic acid ester and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 is 1-6C alkyl; R2 is 2-pyridyl or 4-pyridyl). EXAMPLE:Methyl 4-(2'-pyridyl)-4-cyanopimelate. USE:A raw material for functional polyesters or polyamides having pyridyl groups, e.g. high polymer having pyridyl groups for selective water separation from a water-ethanol mixed system or polymer having catalytic ability in reduction of ketones with NaBH4, etc., or intermediate for agricultural chemicals and medicines. PREPARATION:A pyridylacetonitrile expressed by formula II is reacted with >=2 equivalents, preferably 2-3 equivalents, based on the pyridylacetonitrile expressed by formula II, acrylic acid ester expressed by formula III in or without an inert solvent in the presence of a basic catalyst, e.g. 1,8-diazabicyclo(5.4.0)-7-undecene, at 0-120 deg.C, preferably room temperature to afford the aimed compound expressed by formula I in quantitative yield.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to raw materials for functional polymers having pyridyl groups,
Furthermore, new m4- is useful as an intermediate for agricultural medicines.
The present invention relates to pyridyl-4-cyanopimelic acid ester and a method for producing the same.

Conventional technology As a pimelic acid ester having a substituent at the 4-position and its production method, for example, arylacetonitrile is converted into acrylic acid by heating using a strong base such as sodium ethoxide or Triton B (trade name) as a catalyst. 60-70% of 4-aryl-4-cyanopimelic acid ester by Michael addition to acid ester.
A method is known to obtain a yield of (D, Ledni
cer et al., J. Med, Chem.

1975, 18.593). However, pimelic acid esters having a pyridyl group at the 4-position are not known.

Problems to be Solved by the Invention When attempting to produce 4-pyridyl-4-cyanopimelic acid ester by the reaction of pyridylacetonitrile and acrylic ester using conventional techniques, heating as much as possible was required because pyridylacetonitrile is quite unstable. I need to avoid it.

In addition, sodium ethoxide and Triton (Trito)
n) When a strong base such as H is used, side reactions such as polymerization of acrylic ester and Dickmann condensation of the resulting 4-pyridyl-4-cyanopimelic acid ester occur; No ester was obtained.

The present invention has developed a new substance, 4-
A novel method for producing pyridinyl-4-cyanopimelic acid ester is provided.

Means to Solve the Problem We investigated various bases in the reaction between pyridylacetonitrile and acrylic ester, and found that 1.8-
By using diazabicyclo(5,4,0)-7-undecene as a base catalyst, the reaction can proceed at low temperatures, suppressing side reactions such as acrylic acid ester polymerization and Dickmann condensation, and producing 4-pyridyl-4 - It has been found that cyanopimelic acid ester can be obtained. The present invention will be explained in more detail as follows.

Pyridylacetonitrile represented by general formula (2) % formula % (2) (in the formula, R2 represents a 2-pyridyl group or 4-pyridyl group) and 2
equivalent or more, preferably 2 to 3 equivalents of general formula (3) % formula % (3) (wherein Ro represents a lower alkyl group of C, -C, etc.).

) in an inert solvent such as benzene, toluene, hexane, chloroform, methylene chloride, ethyl ether, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, ethyl acetate, dimethylformamide, or in the absence of a solvent, 1゜8-diazabicyclo(5,4,0) as a catalyst
-7-undecene or its analogous base 1,5
-diazabicyclo(4,3,0)-5-nonene, 1.
By adding 0.1 to 5 mol% of 4-diazabicyclo(2,2,2)octane or the like to pyridylacetonitrile as a catalyst and reacting at 000 to 120°C, preferably at room temperature, the definitions of R and R2 can be defined. 4-pyridinyl-4-cyanopimelic acid ester, which is a new substance represented by the general formula (1) as described above, is quantitatively obtained.

According to the present invention, a novel 4-pyridyl-4-cyanopimelic acid ester was prepared in quantitative yield from pyridylacetonitrile and an acrylic acid ester, which are unstable under relatively mild reaction conditions.

The 4-pyridyl-4-cyanopimelic acid ester thus obtained is, for example, a polymer membrane for selective water separation from a water-ethanol mixed system having a pyridyl group (Yoshikawa et al., P
olym, Preprints, Japan, 1
985°34, 401) or a polymer having a pyridyl group that has catalytic ability in the reduction of ketones by sodium borohydride (Yamaita et al., Polym, Pre
prints.

Japan, 1985. It is highly useful as a raw material for functional polyesters and polyamides, as seen in reports such as (2), 570), and as an intermediate for agricultural medicines.

Effect of the invention The effects of the present invention will be shown in Examples below.

Example 1 1,8-diazabicyclo(
5,4,0) -7-undecene0. Add IJ and add (2-pyridyl)acetonitrile 11.8 ml while stirring! i
' was dissolved in methyl acrylate 8,61 and added dropwise over 30 minutes. During this time, it will generate heat, so cool it down in a water bath.
It was kept at 0°C. Once the fever has subsided, heat the temperature to 80℃.
After heating for an hour, excess methyl acrylate was distilled off under reduced pressure and recovered. 1.8-diazabicyclo(5,4,0)
-7-Undecene was removed by dissolving it in ethyl acetate, passing it through a short layer of silica gel, and distilling off the ethyl acetate to remove methyl 4-(2'-pyridyl)-4-cyanopimelate.26. sP (91% yield) was obtained as an oil.

IR; 2250.1740.1590.1440.12
00.1180cIIL-'NMR (100MHz,
CC4); 8.6δ(IH,m), 7.5-
7.9δ (2H, m), 7.3δ (LH, m),
3.56δ(6H,s).

1.8-2.6δ (8H, m).

Example 2 In the same manner as in Example 1, 4-(
Ethyl 2'-pyridyl)-4-cyanopimelate: n,
9P (100% yield) was obtained as an oil.

IR; 2250.1740.1590.1440.1
200.1180cIrL-'NMR (100MHz
, CC4)', 8.6δ(IH,m), 7.
5-7.9δ (2H, m), 7.3δ (LH, m)
, 4. Qδ(4H+q+J=7Hz), 1.2δ(
6H, t, J = 7Hz), 1.8-2.6δ (8H, m
).

Example 3 Add 70.2f of 1,8-diazabiscif0(5,4,0)-7-undece to 10.4P of methyl acrylate,
14.25' of (4-pyridyl)acetonitrile was added to 20% of methyl acrylate while stirring under water cooling and maintaining the temperature at 20 to 40°C.
0.89- and added dropwise over 20 minutes. 30 minutes later,
The water bath was removed, and the mixture was further stirred at room temperature for 1 hour.

Excess methyl acrylate was recovered by distillation under reduced pressure, and the remaining residue was dissolved in ethyl acetate and passed through a short silica gel layer.
Ethyl acetate was distilled off to obtain methyl 4-(4'-pyridyl)-4-cyanopimelate 351 (yield 99%) as an oil.

IR; 2950.2230.1740.1590.1
430.1200cnL-'NMR (100MHz, C
C4); 8.6δ(2H, m), 7.4δ((2H,
m), 3.58δ (6H, s), 1.9-2.7δ
(8H, m).

Example 4 In the same manner as in Example 3, 4-
Ethyl (4'-pyridyl)-4-cyanopimelate: n
, 7P (yield 99%) was obtained as an oil.

IR; 2950.2230, 1740.1590.1
430.1200crrL-'NMR (100MHz
, C(J4); 8.6δ(2H,m), 7.4
δ(2H, m) + 4-0δ(4H, q, J=7Hz
), 1.9-2.7δ (8H, m), 1.2δ (6
H, t, J = 7Hz).

Example 5 In the same manner as in Example 3, (4-pyridyl)acetonitrile 11.8? and n-hexyl acrylate 471,
n-hexyl 4-(4'-pyridyl)-4-cyanopimelate 42.3? (yield 98%) was obtained as an oil.

IR; 2950.2230.1740.1590.1
430.1200crrL-'NMR (100MHz
, CCl4); 8.6δ(2H,m), 7
．． 4δ (2H, m), 4.1δ (4H, t, J=7Hz
), 1.9-2.7δ (8H, m), 0.8-1.8δ
(22H, m).

Claims (1)

[Claims] 1) General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R_1 represents a lower alkyl group of C_1 to C_6, and R_2 represents a 2-pyridyl group or a 4-pyridyl group. - represents a pyridyl group.) 4-pyridyl-4-cyanopimelic acid ester. 2) Pyridylacetonitrile represented by general formula (2) R_2CH_2CN (2) (wherein R_2 represents a 2-pyridyl group or 4-pyridyl group) and general formula (3) CH_2=CHCO_2R_1 (3) (formula In the reaction with the acrylic acid ester represented by R_1 represents a lower alkyl group of C_1 to C_6, 1,8-diazabicyclo(5,4,0,)-7-undecene is used as a base catalyst. Characteristic general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, R_1 and R_2 are the same as above) A method for producing 4-pyridyl-4-cyanopimelic acid ester.