JPS6212744A - Novel allenecarboxylic acid ester and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is hydrocarbon residue; R2-R4 are H or hydrocarbon residue; R2 and R3 may be chain or together form a ring). EXAMPLE:Methyl-2,3-butadienoate. USE:Pharmaceuticals, agricultural chemicals and their intermediates. Since the allene bond can be isomerized to conjugated diene with acid or alkali, the compound is useful as a raw material for a conjugated diene ester monomer. PREPARATION:The compound of formula I can be produced by contacting the propargyl compound of formula II with a platinum-group compound catalyst [e.g. tris(tribenzylideneacetylacetone)dipalladium] in the presence of carbon monoxide. The amount of the catalyst is usually 0.01-10mol, preferably 0.1-5mol of the platinum-group metal compound per 100mol of the raw material. The partial pressure of carbon monoxide is usually 1-100atm and the reaction temperature is preferably 20-100 deg.C.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a new allene carboxylic acid ester and a method for producing the same, and more particularly, allene carboxylic acid ester is produced by a novel reaction using a gulono-4 gylcargenate compound as a starting material. Concerning a method of manufacturing.

(Prior art) Allene compounds with allene bonds are highly reactive substances) and are useful as raw materials for medicines, agricultural chemicals, industrial chemicals, etc.! be.

As a result of intensive research into an efficient method for producing such allene compounds, the present inventors have discovered that allene carboxylic acid esters, which have not been described in literature, can be efficiently obtained by using a novel reaction using gulono-4-gylcargenate as a raw material. The present invention has been completed.

(Means for Solving the Problems) Thus, according to the present invention, a novel allene carmenic acid ester represented by the following general formula (1) is provided as a first invention, and a novel allene carmenic acid ester represented by the following general formula (1) is provided as a second invention. A method for producing an allene carboxylic acid ester is provided, which comprises contacting a blockgyl compound represented by II) with a platinum group metal compound catalyst in the presence of carbon monoxide.

(In the formula, R2 represents a hydrocarbon residue, R2, R5, and R4 represent hydrogen or a hydrocarbon residue, and R2 and R3 may be chain-like or a combination of the two may form a ring. ) In the present invention, a propargyl compound represented by the general formula (...) is used as a starting material. R1 in the above formula
may be an aliphatic residue, an alicyclic residue, or an aromatic residue, but usually a lower alkyl group such as a methyl group, ethyl group, propyl group, or butyl group is used. Also R2 and R
Specific examples of 3 include hydrogen atoms, lower alkyl groups as mentioned above, long chain alkyl groups such as octyl group and decyl group, alkenyl groups such as prenyl group, phenyl group,
Examples include aryl groups such as a benzyl group, and the two may also be bonded to form a ring such as a cyclopentane ring, a cyclohexane ring, or a cyclooctane ring. Specific examples of R4 include, in addition to a hydrogen atom, the same alkyl groups, alkenyl groups, and aryl groups as mentioned above. The number of carbon atoms in R2, R3, and R4 is not particularly limited, but usually the total number of carbon atoms is 100 or less, and from the viewpoint of reactivity, it is preferably 50 or less, and <K30 or less.

In the present invention, a platinum group metal compound,
Preferably, a catalyst consisting essentially of a platinum group metal compound and a ligand is used. The platinum group metal compound is a salt or complex of radium, ruthenium, platinum, rhodium, etc., and specific examples include tris(dibenzylideneacetone)2/4'radium(o), tris(tribenzylideneacetylacetone), tris(tribenzylideneacetylacetone), etc. ) Minochu Radium (0),
Palladium acetate, palladium propionate, 9-radium butyrate, palladium benzoate, / mother radium acetylacetonate, palladium nitrate, radium sulfate, chloride radium, dihydrotetrakis (triphenylphosphine) ruthenium, ruthenium acetylacetonate , platinum acetate, platinum acetylacetonate, and the like.

Among the platinum group metals, palladium is preferable in terms of reactivity, and it is particularly preferable to use zero-valent olefin complexes or divalent organic compounds.

In addition, the ligands to be included are listed in V of the periodic table as coordination factors.
An electron-donating compound containing a group element, namely nitrogen, phosphorus, arsenic or antimony, specific examples of which are biricin, quinoline, trimethylamine, triethylamine, tributylamine, α,α'-dipyridyl, 1,10
-7 Nitrogen-containing compounds such as enanthroline; triethylphosphine, tri-n-butylphosphine, triphenylphosphine, tri-rotolylphosphine, tri-p-biphenylphosphine, tri-methoxyphenylphosphine, phenyldiphenoxyphosphine, triethylphosphite , tri-butyl phosphite, tri-n-hexyl phosphite, triphenyl phosphite, tri-n-hexyl phosphite, triphenyl thiophosphite, α, β-ethylene di(diphenyl) phosphine, α, β-ethylene di Arsenic-containing compounds such as (diethyl)phosphine, α,β-ethylenedi(diptyl)phosphine, etc.; Arsenic-containing compounds such as triethylarsenic, triptylarsenic, triphenylarsenic; Antimony-containing compounds such as tripropylantimony, triphenylantimono, etc. Examples include compounds. Above all, tv phosphorus compounds are preferred in terms of reaction activity, selectivity, economy, and the like.

The amount of such a ligand used is usually 0.1 mol or more per 1 mol of the platinum group metal compound, and from the viewpoint of reaction activity, it is preferably used in an amount of 1 mol or more, particularly 2 to 20 mol.

The amount of catalyst used in the present invention is appropriately selected, but usually 0.01-1 mol of platinum group metal compound per 100 mol of raw material.
It is used in such a proportion that it is 0 mol, preferably 0.1 to 5 mol. Further, the platinum group metal compound and the ligand may be reacted in advance.

Usually, a catalyst is prepared by bringing each component into contact in a reaction system.

In the present invention, the reaction is carried out in the presence of -carbon oxide. The partial pressure of carbon monoxide in the system is not limited to <K, but is usually 1 to 100 atmospheres. The reaction temperature is usually 0°C or higher, preferably 20 to 100°C, and the reaction time is usually 5 minutes to 30 hours.

Further, a diluent may be present during the reaction, and specific examples include amides such as dimethylformamide, dimethylformamide, dimethylacetamide, dimethylpropioamide, N-methylpyrrolidone, etc.; methanol, ethanol, propatool, ter -Alcohols such as butanol, ethylene glycol, diethylene glycol monoethyl ether, etc. are exemplified, and alcohols are particularly prized.

These diluents are generally used in such a proportion that the concentration of the starting materials is 1 to 50% by weight, and their use can improve reaction activity and catalyst stability.

After the reaction is completed, the target product is separated from the reaction solution by conventional methods such as solvent extraction, distillation, recrystallization, etc., thereby obtaining a highly pure allene carboxylic acid ester.

Arencar thus obtained? Acid esters are compounds having various structures, such as aliphatic, alicyclic, or aromatic, and are useful as industrial chemicals, pharmaceuticals, agricultural chemicals, intermediates thereof, and the like. Furthermore, since the arene bond can be easily isomerized to a conjugated diene with an acid or an alkali, it is useful as a raw material for a conjugated tsene-based ester heptamer.

(Effects of the Invention) Thus, according to the present invention, by utilizing a novel reaction, it is possible to obtain an allene carboxylic acid ester, which is a novel compound, with high activity and high selectivity.

(Example) The non-invention will be explained in more detail with reference to Examples below.

Example 1 3 mmol of carbonic acid (1-ethynylcyclohexyl) methyl ester, 0.03 mmol of tris(tribenzylideneacetylacetone)nipalladium, 0.24 mmol of triphenylphosphine, and 6 ml of methanol were charged in a reactor, and the partial pressure was 15. The mixture was stirred at 50° C. for 14 hours under a carbon monoxide atmosphere at atmospheric pressure. After the reaction, methanol was distilled off under reduced pressure, and methylene chloride was added to the residue, followed by washing with saturated brine. After concentrating the solvent, the residue was purified by silica dal chromatography to obtain 2-methoxycal diruethenylidenecyclohexane in a yield of 96 mol.

. NMR (90MH2, CDCt3): δ=1.40
-2.00 (m -6H--CH2-) -2,OO
-2,40(m, 4H, ==c-ca2-),
3.71 (a-3H.

-0CHs ) -5,40-5,58(m -I H
-=CH-). C-NMR (22,5 MHz, CDCt
, ) δ = 25.8 (C-4), 26.9 (C-3), 3
0.2 (C-2), 51.7 (C-8), 85.5 (C
-6).

106.7 (C-1), 167.1 (C-2), 207
．． 6(C-4)0IR(neat) 2920.2850.1960(C=C=C), 172
0′(,:”C==0), 1630.144
0,1260.1190°1155 (crR-') Example 2 Except that dimethylformamide was used instead of methanol, 0.06 mmol of palladium acetate was used as the /fragilam compound, and the reaction time was 12 hours. When an experiment was conducted in the same manner as in Example 1, 2-methoxycar? Nylethenylidenecyclohexane was obtained in a yield of 70 mol.

Example 3 α, β-ethylene di(
An experiment was carried out in the same manner as in Example 1 except that (diphenyl)phosphine was used, and 2-methoxycardenylethenylidenecyclohexane was obtained in a yield of 60 mol.

Example 4 An experiment was conducted in the same manner as in Example 1 except that the compounds shown in Table 1 were used as starting materials and the reaction conditions shown in Table 1 were used. The results are shown in Table 1.

The physical properties of the product are as follows.

(Experiment number 1) Methyl-2,3-butadienoate”
HNMR (CDCl-5-90MHz) 3.75
←a, 3H.

-0CH3) 5.23 (d, J=6.4Hz,
2H, =CH2)5.66(t, J=6.4Hz, IH
,=CH-)01'CNMR(CDCts-22,5
M) Iz ) 52.1 (C5) -79,2 (C4
), 87.7 (C2), 166.1 (C1).

215.8 (C3).

(Experiment No. 2) Methyl-2-etheridenonanoate” H-NMR (90MHz-CDCLs) δ=0
．． 70-1.88(rn, 13H,-CI(2-,-
CH,).

2.00-2.48 (m, 2H--CH2-)
, 3-73 (5-3H, -OCH,), 5.11 (
t, =CH2, J=3. OH1)OC-NMR(22
, 5MHz - CDCLs) δ=14.1, 22.
7, 28.1, 28.2, 29.2, 31.9°52.0 (C-5), 78.8 (C-4),
100.3 (C-2).

167.7 (C-1), 214.0 (C-3)' IR
(net) 2950.2930.2850.1970 (C=C=C
).

1945.1725 (, -C=0), 1440.126
5゜850 (=C=CH2) (sub-1) (Experiment number 3) Methyl-4,8-dimethyl-2,3,7
-Nonadrienoate 01c-NMR (90MH2, CDCl3) δ=1.6
0 (1,3H,=C(CH3)2), 1.68(
1.

aH,=c-(aH3)2'), 1.79 (d
, 3H,=CH(CH,)-.

J=2.9 Hz) -1,94-2,45(m-4
H, -CH2-) -3,72(s * 3 H--0
CHs), 4.92-5.28 (m-'I H
, =CH-) = 5.40-5.64(m, IH,
=C=CH-)1' o IR(neat) 2930.2900.2850.1960(C=C=C
).

1720 (C=C-CO-), 1635.1435,
1400°1255.1155.1030.830,7
35(cya-') (Experiment No. 4) Methyl-4-methyl-2,3-decagenoate o' H-NMR (90hliz-CDCA3)
-δ=0.72-1.68 (m, IIH, -CH
2-, -CH5).

1.78 (d, 3H, C=C-CH3-J=2
．． 9 Hz) -1,90-2,20(m-2H-
C=C-CHz-), 3.71(fi, 3H,
-OCH,) $ 5.50 (tq, 1H-C=CH
−.

J”2.9, 2.9 Hz) O”C-NMR (22.5 MHz, CDCl3)
δ=14.0 (C-10), 17.9 (C-11), 2
2.7゜27.1.28.8, 31.7, 33.2 (C
-5), 51.7 (C-12), 86.9 (C-4),
104.5 (C-2).

167.1 (C-1), 210.5 (C-3) o IR
(neat) 2950.2925, 2850.1965 (C=C=C
).

1725 (:C士O), 1435, 1400゜1260
(C-0), 1190, 1160.1035.
:910.830.720(m-') (Experiment No. 5) Methyl-4-phenyl-2,3-1°butagenoate" HNMR (CDCts, 90hliz) -
3,73(s-3H-0CH3) '6.0
1 (d, J=6.4H-z, IH,=CH-
)−6,60(d, [J =6.4 Hz
-I Hs =CH-)-7,28(s -5H, @
). 11・

Claims (1)

[Claims] 1. An allene carboxylic acid ester represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1 is a hydrocarbon residue, R_2, R_3, R_
4 represents hydrogen or hydrocarbon residue, R_2 and R_3
may be chain-like or a combination of both may form a ring. ) 2. Production of an allene carboxylic acid ester represented by the above general formula (I), which is characterized by contacting a propargyl compound represented by the following general formula (II) with a platinum group metal compound catalyst in the presence of carbon monoxide. Law. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R_1, R_2, R_3 and R_4 are the same as above.)