JP2002226454A - Method for producing beta-arylthioacrylic ester derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for easily and efficiently producing a beta- arylthioacrylic ester derivative using starting materials readily available or synthesizable by simple operations, and to provide the above derivative obtained by the above method. SOLUTION: This method for producing a beta-arylthioacrylic ester derivative is characterized by comprising reaction between an acetylene compound and a thiocarbonic ester in the presence of a metal complex catalyst, especially a transition metal complex catalyst containing palladium or rhodium or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for efficiently producing a beta-arylthioacrylate derivative capable of performing a wide range of chemical transformations based on the reactivity of a sulfur-carbon bond. These compounds are widely used, for example, as hormones, sex pheromones, food inhibitors for insects, and synthetic intermediates of other bioactive compounds.

[0002]

2. Description of the Related Art As a method for synthesizing a beta-arylthioacrylic acid ester derivative, a method of causing a thiol to act on an acetylene carboxylic acid derivative and a method of causing a thiol to act on a beta keto acid ester have been known. Except for these, synthesis of acetylene carboxylic acid derivatives and beta keto acid esters is not easy, and it is hardly considered to be an industrially advantageous method.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned situation, and is intended to facilitate and efficiently use a starting material which is easily available or can be synthesized by a simple operation. An object of the present invention is to provide a novel method for producing a beta-arylthioacrylic acid ester derivative capable of producing a ruthioacrylic acid ester derivative, and a novel beta-arylthioacrylic acid ester derivative obtained by the method.

[0004]

According to the present invention, there is provided a compound of the general formula (II) R ¹ C≡CH (II) wherein R ¹ has a substituent in the presence of a metal complex catalyst. Good alkyl group, cycloalkyl group optionally having substituent (s), alkenyl group optionally having substituent (s), cycloalkenyl group optionally having substituent (s), optionally having substituent (s) A good aryl group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, or a silyl group which may have a substituent.) With the general formula (III) ArSCOOR ² (III) (wherein R ² is an alkyl group which may have a substituent,
An aryl group which may have a substituent or an aralkyl group which may have a substituent is represented, and Ar represents an aryl group which may have a substituent. Wherein R ¹ (ArS) C ＝ CHCOOR ² (I) (wherein R ¹ , R ² and Ar are the same as those described above). )).

Further, the present invention has the general formula ^{_{(I ') R 0 1 (}} ArS) C = CHCOOR 2 (I') ( _{wherein, R} ^{0 1} is an alkyl group optionally having a substituent, A cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an aralkyl group which may have a substituent, A heterocyclic group which may have a substituent,
A silyl group or a substituted aryl group which may have a substituent, wherein R ² is an alkyl group which may have a substituent,
An aryl group which may have a substituent or an aralkyl group which may have a substituent is represented, and Ar represents an aryl group which may have a substituent. )).

That is, the present inventors have made intensive studies to achieve the above object, and as a result, thiocarbonate was converted to acetylene in the presence of a metal complex catalyst, particularly a transition metal complex catalyst such as palladium or rhodium. The inventors have found that the compound easily attaches to a bond, and have completed the present invention in which an easily available acetylene compound and a thiocarbonate ester that can be synthesized by a simple operation are reacted in the presence of a metal complex catalyst.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formulas (I) and (II), the alkyl group of the optionally substituted alkyl group represented by R ¹ has, for example, 1 to 20 carbon atoms.
Preferably a linear or branched alkyl group of 1 to 10, more preferably 1 to 6, and more specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Examples include an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, and a hexyl group.
Examples of the cycloalkyl group of the cycloalkyl group which may have a substituent include, for example, a monocyclic, polycyclic or condensed ring having 3 to 30, preferably 3 to 20, and more preferably 3 to 10 carbon atoms. Examples include the cycloalkyl group of the formula, more specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. Examples of the alkenyl group of the alkenyl group which may have a substituent include, for example, one of the above-mentioned alkyl groups having 2 or more carbon atoms.
Examples thereof include those having an unsaturated group such as two or more double bonds, and more specifically, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-
Butadienyl group, 2-pentenyl group, 2-hexenyl group and the like. Examples of the cycloalkenyl group of the cycloalkenyl group which may have a substituent include those having an unsaturated group such as one or more double bonds in the cycloalkyl group described above, and more specifically, Examples include a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, and the like. Examples of the aryl group of the aryl group which may have a substituent include, for example, a monocyclic, polycyclic or condensed-ring aromatic having 6 to 30, preferably 6 to 20, and more preferably 6 to 14 carbon atoms. Examples thereof include a hydrocarbon group, and more specifically, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and the like. Examples of the aralkyl group of the aralkyl group which may have a substituent include, for example, a monocyclic, polycyclic or condensed aralkyl group having 7 to 30, preferably 7 to 20, and more preferably 7 to 15 carbon atoms. And more specifically, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and the like.

Examples of the substituent of the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group include, for example, a hydroxyl group such as an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group; For example, chlorine, bromine, halogen atoms such as fluorine, cyano groups such as dimethylamino group, dialkylamino groups such as diethylamino group, silyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group and the like , For example, a siloxy group of a t-butyldimethylsiloxy group.

The heterocyclic group of the heterocyclic group which may have a substituent includes at least one nitrogen atom in the ring,
It has an oxygen atom or a sulfur atom, and the size of one ring is 5 to 5.
20 members, preferably 5 to 10 members, more preferably 5 to 7 members
And a saturated or unsaturated monocyclic, polycyclic or condensed cyclic group which may be condensed with a carbocyclic group such as a cycloalkyl group, a cycloalkenyl group or an aryl group. Specifically, for example, pyridyl group, thienyl group, thiazolyl group, furyl group, piperidyl group, piperazyl group, morpholino group, imidazolyl group, indolyl group,
Examples include a quinolyl group and a pyrimidinyl group. Further, as the substituent of the heterocyclic group, for example, an alkyl group, a hydroxyl group, for example, a methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as a butoxy group, for example, chlorine, bromine, a halogen atom such as fluorine, a cyano group, for example, Dimethylamino group, dialkylamino group such as diethylamino group, silyl group, for example, trimethylsilyl group, triethylsilyl group,
Substituted silyl groups such as a t-butyldimethylsilyl group and a triphenylsilyl group, for example, a siloxy group of a t-butyldimethylsiloxy group and the like. As the substituted silyl group,
Examples include those in which 1 to 3 hydrogen atoms of a silyl group are replaced by an alkyl group, an aryl group, and the like. Among them, a tri-substituted product is preferable, and more specifically, a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl Group, triphenylsilyl group and the like.

In the general formulas (I) and (III), R ²
As the alkyl group of the alkyl group which may have a substituent, the aryl group of an aryl group which may have a substituent, and the alkyl group of an aralkyl group which may have a substituent, And the same as the alkyl group, the aryl group, and the aralkyl group in R ¹ described above. In addition, the same substituents as those described above for R ¹ can also be used. In the general formulas (I) and (III), examples of the aryl group of the aryl group which may have a substituent represented by Ar include, for example, C 6 to C 30,
Preferably 6 to 20, more preferably 6 to 14 monocyclic rings,
Examples include a polycyclic or fused cyclic aromatic hydrocarbon group, and more specifically, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and the like. Examples of the substituent include the same substituents as those of the aryl group in R ¹ described above.

[0011] In the general formula (I '), R ₀ ¹ alkyl group which may have a substituent group represented by which may have a substituent cycloalkyl group, which may have a substituent A good alkenyl group, a cycloalkenyl group which may have a substituent, an aralkyl group which may have a substituent,
The silyl group which may have a heterocyclic group and a substituted group may have a substituent, include exactly the same as those in the R ^1. Examples of the substituted aryl group include a hydroxyl group such as a methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as a butoxy group, a chlorine atom, a bromine atom, a halogen atom such as a fluorine atom, a cyano group such as a dimethylamino group, and a diethylamino group. Having a substituted silyl group such as a dialkylamino group, a silyl group such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triphenylsilyl group, such as a siloxy group such as a t-butyldimethylsiloxy group; ,
For example, aryl groups such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group and a biphenyl group can be mentioned.

The molar ratio of the acetylene compound represented by the general formula (II) to the thiocarbonate represented by the general formula (III) is not particularly limited, but is usually 1: 1. Yes, larger or smaller does not inhibit the occurrence of the reaction, but when considering the yield based on expensive acetylene compounds, it is best to use thiocarbonate in excess of acetylene. preferable.

In order for the reaction of the present invention to proceed efficiently,
The presence of a metal complex catalyst, especially a transition metal complex catalyst, is essential; in the absence of a catalyst, the reaction does not proceed or becomes very slow. As the catalyst, those having various structures can be used, and preferable ones are those having a low valence, and a transition metal complex to which various ligands are coordinated can be used. Particularly preferred transition metals include palladium and rhodium. For the palladium catalyst, a zero-valent complex having a tertiary phosphine or a tertiary phosphite as a ligand, and for a rhodium complex, a monovalent complex is more preferable. It is also a preferred embodiment to use an appropriate precursor complex which is easily converted to a low-valent complex in the reaction system. Further, a tertiary phosphine or a tertiary phosphite is used as a ligand in combination with a tertiary phosphine or a tertiary phosphite and a transition metal complex containing no tertiary phosphine or a tertiary phosphite as a ligand. Is also a preferred embodiment. Various tertiary phosphines and tertiary phosphites are examples of ligands that exhibit advantageous performance in any of these methods.

Illustrates ligands that can be suitably used
Then, triphenylphosphine, diphenylmethylphos
Fin, phenyldimethylphosphine, tricyclohexene
Silphosphine, triisopropylphosphine, 1,4
-Bis (diphenylphosphino) butane, 1,3-bis
(Diphenylphosphino) propane, 1,2-bis (di
Phenylphosphino) ethane, 1,1'-bis (dife
Nylphosphino) ferrocene, trimethylphosphite
And triphenyl phosphite. this
Tertiary phosphine or tertiary phosphine used in combination with
Complexes that do not contain phyte as a ligand include bis
(Dibenzylideneacetone) palladium complex, paraacetic acid
Diium complex, (π-cyclopentadienyl) (π-ant
L) palladium complex, chloro (1,5-cyclooctadi)
Ene) rhodium complex, chloro (norbornadiene) rhodium
Complex, (acetylacetonato) dicarbonyl rhodium
Complex [Rh (acac) (CO)₂]
It is not limited to these. Also preferably used
Phosphine complex or phosphite complex
Tylbis (triphenylphosphine) palladium complex
[PdMe₂(PPh₃)₂], Dimethylbis (trimethy
Ruphosphine) palladium complex [PdMe₂(PMe ₃)
₂], Dimethylbis (diphenylmethylphosphine)
Radium complex, dimethylbis (phenyldimethylphosphine
In) palladium complex [PdMe₂(PPhM
e₂)₂], Bis (tricyclohexylphosphine)
Radium complex [Pd (PCy₃)₂], (Ethylene) bis
(Triphenylphosphine) palladium complex, tetrakis
(Triphenylphosphine) palladium complex [Pd
(PPh₃)₄], Chlorotris (triphenylphosphite)
N) Rhodium complex [RhCl (PPh₃)₃], Carboni
Lechlorobis (triphenylphosphine) rhodium complex
[RhCl (CO) (PPh₃)₂], Chloro (1,5-si
(Crooctadiene) (triphenylphosphine) rhodium
Complex [RhCl (cod) (PPh₃)].
These transition metal catalysts may be any one suitable for the reaction.
A species or two or more species are appropriately selected and used.

The amount of these transition metal complexes to be used may be a so-called catalytic amount, which is 20 mol% or less, usually 5 mol% or less based on the acetylene compound.

The reaction does not require the use of a solvent, but can be carried out in a solvent if necessary. Examples of the solvent include hydrocarbon solvents such as benzene, toluene, xylene, n-hexane, and cyclohexane, or
For example, ether solvents such as dimethyl ether, diethyl ether, diisopropyl ether, 1,4-dioxane, and tetrahydrofuran are generally used. Although the reaction temperature depends on the structure of the acetylene compound, it is generally preferable to heat the reaction to 50 ° C. or higher, and usually to 80 to 20 ° C.
It is selected from the range of 0 ° C. Although this reaction proceeds even in the presence of oxygen such as in air, the reaction intermediate is slightly sensitive to oxygen, and therefore it is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen, argon, or methane. Isolation and purification of the product from the reaction mixture can be easily achieved by a method known per se, such as chromatography, distillation or recrystallization, which is commonly known in the art.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

Example 1 Pd (PCy ₃ ) ₂ (0.04 mmol) and S-phenyl O-methylthiocarbonate (1.2 mmol) were added to octane (2 ml) to produce a pale red solution. 1-Octin (1.0 mmol) was added thereto, and the mixture was heated at 110 ° C for 20 hours under a nitrogen atmosphere. After cooling the reaction mixture, it was analyzed by gas chromatography.
Methyl (Z) -3-phenylthio-2-nonenoate and positional isomers in which the addition direction of the phenylthio group and the ester group to the acetylene bond are reversed are produced in a total yield of 86%, and the isomer ratio of both isomers Was 98: 2. The reaction solution was concentrated and subjected to column chromatography (developed with silica gel and hexane) to obtain (Z) with an isolation yield of 71%.
Methyl -3-phenylthio-2-nonenoate (Product 3
a) was obtained. This compound is a novel compound which has not been described in any literature, and its properties, physical properties, spectrum data and the like are as follows. Colorless liquid; boiling point 135 ° C (0.25 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.54-7.51 (m, 2H), 7.38-7.33 (m, 3H), 5.83 (s, 1H, C =
CH), 3.73 (s, 3H , OCH 3), 2.08 (t, 2H, J = 7.7 Hz), 1.
34-1.00 (m, 8H), 0.78 (t, 3H, J = 7.1Hz). ¹³ C NMR (C
DCl ₃ ) δppm 166.6 (COOCH ₃ ), 162.6 (C = CH), 135.9, 130.7, 129.3,
129.0,111.1 (C = CH), 51.1 (COOCH 3), 36.6, 31.2, 29.
2, 28.4, 22.3, 13.9. IR (liquid film) 2954, 2932, 2862, 1707, 1582, 1439, 1197, 1025, 75
2 cm- ¹ . GC-MS m / z (relative intensity) 278 (M ⁺ , 11), 247 (9), 219 (5), 208 (35), 147 (24), 13
4 (100), 110 (57), 67 (39), 59 (41). Elemental analysis (C ₁₆ H ₂₂ O ₂ as S) Calculated: C, 69.07; H, 7.91 ; S, 11.53. Found: C, 69.34; H, 8.17; S, 11.42.

Examples 2 to 13 Table 1 summarizes the results obtained by reacting various acetylenes in the same manner as in Example 1. However, unless otherwise specified, a 1: 3 mixed solvent of toluene and octane was used.

[0020]

[Table 1]

Among the products obtained in these examples, the spectroscopic and / or elemental analysis data of the novel compounds were as follows.

Product 3b: (Z) -3-phenylthio-
Methyl 2-heptenoate Colorless liquid; boiling point 110 ° C. (0.15 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.55-7.52 (m, 2H), 7.39-7.33 (m, 3H), 5.84 (s, 1H, C =
CH), 3.74 (s, 3H , OCH 3), 2.08 (t, 2H, J = 7.7Hz), 1.36
-1.24 (m, 2H), 1.09-1.02 (m, 2H), 0.67 (t, 3H, J = 7.3 H
z). ¹³ C NMR (CDCl ₃ ) δ ppm 166.7 (COOCH ₃ ), 162.6 (C = CH), 136.0, 130.6, 129.3,
129.0,111.1 (C = CH), 51.2 (COOCH 3), 36.3, 31.3, 21.
9, 13.5. IR (liquid film) 2932, 2862, 1707, 1582, 1439, 1180, 1021, 752 cm
^-1 . GC-MS m / z (relative intensity) 250 (M ⁺ , 16), 219 (15), 208 (43), 189 (24), 175 (3), 1
47 (28), 134 (100), 110 (71), 65 (36), 59 (39). Elemental analysis (C ₁₄ H ₁₈ O ₂ as S) Calculated: C, 67.20; H, 7.20 ; S, 12.80. Found: C, 67.35; H, 6.99; S, 12.42.

Product 3c: (Z) -3-phenylthio-
Methyl 2-butenoate Colorless liquid; boiling point 50 ° C. (0.15 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.56-7.53 (m, 2H), 7.41-7.34 (m, 3H), 5.85 (q, 1H, J = 1.0 Hz, C = CH), 3.74 (s, 3H, OCH ₃ ), 1.8
1 (d, 3H, J = 1.0Hz). ¹³ C NMR (CDCl ₃ ) δ ppm 166.6 (COOCH ₃ ), 158.7 (C = CH), 136.1, 130.8, 129.5,
129.1,111.5 (C = CH), 51.2 (COOCH 3), 25.1. IR (liquid film) 1705, 1593, 1441, 1197, 1046, 754 cm ^-1 . GC-MS m / z (relative intensity) 208 (M ⁺ , 23), 193 (1), 177 (28), 149 (100), 134 (31),
110 (56), 65 (43), 59 (58). Elemental analysis (C ₁₁ H ₁₂ O ₂ as S) Calculated: C, 63.46; H, 5.77 ; S, 15.38. Found: C, 63.36; H, 6.00; S, 14.97.

Product 3d: methyl (Z) -4,4-dimethyl-3-phenylthio-2-pentenoate colorless liquid; boiling point 100 ° C. (0.15 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.31-7.14 (m, 5H), 6.23 (s, 1H, C = CH), 3.32 (s, 3H, O
_{CH 3), 1.29 (s,} 9H). ¹³ C NMR (CDCl ₃ ) δ ppm 166.0 (COOCH ₃ ), 161.4 (C = CH), 136.6, 129.4, 128.8,
126.2, 119.6 (C = CH), 51.1 (COOCH ₃ ), 39.9, 29.2. IR (liquid film) 2972, 2870, 1734, 1611, 1481, 1439, 1195, 1172, 74
5,688 cm- ¹ . GC-MS m / z (relative intensity) 250 (M ⁺ , 17), 219 (8), 193 (18), 149 (25), 135 (26), 1
09 (38), 101 (34), 81 (39), 65 (24), 57 (100). Elemental analysis (C ₁₄ H ₁₈ O ₂ as S) Calculated: C, 67.20; H, 7.20 ; S, 12.80. Found: C, 66.86; H, 7.15; S, 12.84.

Product 3e: methyl (Z) -7-tert-butyldimethylsiloxy-3-phenylthio-2-heptenoate colorless liquid; boiling point 160 ° C. (5.2 × 10 ^-4 Torr). ¹ H NMR (C ₆ D ₆ ) δ ppm 7.34-7.31 (m, 2H), 6.93-6.88 (m, 3H), 5.98 (s, 1H, C =
CH), 3.47 (s, 3H , OCH 3), 3.24 (t, 2H, J = 6.2Hz) 1.98
(t, 2H, J = 7.5Hz), 1.37-1.13 (m, 4H), 0.93 (s, 9H),-
0.008 (s, 6H). ¹³ C NMR (CDCl ₃ ) δ ppm 166.7 (COOCH ₃ ), 162.3 (C = CH), 135.9, 130.6, 129.3,
129.0,111.2 (C = CH), 62.5 , 51.2 (COOCH 3), 36.4, 31.
9, 25.9, 25.6, 18.3, -5.32. IR (liquid film) 2952, 2860, 1711, 1582, 1197, 1100, 835, 777 cm
^-1 . GC-MS m / z (relative intensity) 365 (M ⁺ -Me, 1), 349 (2), 323 (70), 291 (51), 217 (12),
189 (24), 147 (23), 109 (15), 89 (100), 75 (55), 59 (3
7). Elemental analysis (C ₂₀ H ₃₂ O ₂ as SSi) Calculated: C, 63.16; H, 8.42 . Found: C, 62.92; H, 8.57.

Product 3f: (Z) -4-methoxy-3-
Methyl phenylthio-2-butenoate Colorless liquid; boiling point 100 ° C. (0.2 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.58-7.55 (m, 2H), 7.41-7.33 (m, 3H), 6.13 (s, 1H, C =
CH), 3.76 (s, 3H), 3.71 (s, 2H), 3.16 (s, 3H). ¹³ C NMR (CDCl ₃ ) δ ppm 166.7 (COOCH ₃ ), 155.8 (C = CH), 135.9, 131.2, 129.6,
129.1, 110.8 (C = CH), 73.5, 58.4, 51.4. IR (liquid film) 2932, 1707, 1597, 1439, 1313, 1195, 1123, 752 cm
^-1 . GC-MS m / z (relative intensity) 238 (M ⁺ , 13), 206 (56), 191 (63), 176 (4), 147 (38), 1
34 (20), 110 (100), 101 (25), 91 (21), 69 (73), 59 (36). Elemental analysis (C ₁₂ H ₁₄ O ₃ as S) Calculated: C, 60.50; H, 5.88 ; S, 13.40. Found: C, 60.28; H, 5.73; S, 13.09.

Product 3 g: (Z) -4-hydroxy-4
-Methyl-3-phenylthio-2-pentenoate Colorless liquid; boiling point 85 ° C (0.15 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.35-7.17 (m, 5H), 6.59 (s, 1H, C = CH), 3.39 (s, 3H, O
_{CH 3), 2.20 (s,} 1H), 1.52 (s, 6H). ¹³ C NMR (CDCl ₃ ) δ ppm 165.8 (COOCH ₃ ), 158.1 (C = CH), 135.3, 129.6, 129.0,
126.7,120.9 (C = CH), 174.9 , 51.3 (COOCH 3), 29.1. IR (liquid film) 3436, 2980, 2953, 1715, 1618, 1481, 1462, 1296, 11
78, 1025, 745, 690 cm- ¹ . GC-MS m / z (relative intensity) 252 (M ⁺ , 9), 237 (1), 221 (2), 194 (34), 163 (22), 135
(100), 117 (12), 85 (14), 65 (9), 59 (33). Elemental analysis (C ₁₃ H ₁₆ O ₃ as S) Calculated: C, 61.89; H, 6.35 ; S, 12.72. Found: C, 61.54; H, 6.66; S, 12.57.

Product 3h: methyl (Z) -6-chloro-3-phenylthio-2-hexenoate colorless liquid; boiling point 100 ° C. (0.2 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.55-7.52 (m, 2H), 7.45-7.36 (m, 3H), 5.90 (s, 1H, C =
CH), 3.75 (s, 3H , OCH 3), 3.30 (t, 2H, J = 6.3Hz), 2.31
(t, 2H, J = 7.4Hz), 1.77 (m, 2H). ¹³ C NMR (CDCl ₃ ) δ ppm 166.4 (COOCH ₃ ), 160.0 (C = CH), 135.8, 130.3, 129.5,
129.2,112.4 (C = CH), 51.3 (COOCH 3), 43.4, 33.6, 31.
Five. IR (liquid film) 3062, 2952, 1707, 1582, 1439, 1199, 1025, 752, 692
cm ^-1 . GC-MS m / z (relative intensity) 270 (M ⁺ , 10), 239 (5), 211 (20), 189 (17), 176 (9), 16
1 (24), 147 (29), 134 (30), 110 (100), 97 (9), 77 (19), 6
5 (67), 59 (51). Elemental analysis (C ₁₃ H ₁₅ ClO ₂ as S) Calculated: C, 57.67; H, 5.54 ; S, 11.83. Found: C, 57.60; H, 5.74; S, 12.12.

Product 3i: methyl (Z) -6-cyano-3-phenylthio-2-hexenoate colorless liquid; boiling point 130 ° C. (0.2 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.54-7.25 (m, 5H), 5.89 (s, 1H, C = CH), 3.75 (s, 3H, O
CH ₃ ), 2.30 (t, 2H, J = 7.4 Hz), 2.13 (t, 2H, J = 7.1 Hz),
1.65 (m, 2H). ¹³ C NMR (CDCl ₃ ) δ ppm 166.2 (COOCH ₃ ), 158.8 (C = CH), 135.6, 130.1, 129.7,
129.4,118.7 (CN), 113.1 (C = CH), 51.4 (COOCH ₃ ), 35.1,
24.5, 16.1. IR (liquid film) 2952, 2250, 1705, 1582, 1439, 1201, 754, 694 cm
^-1 . GC-MS m / z (relative intensity) 261 (M ⁺ , 15), 230 (14), 202 (45), 189 (39), 161 (13),
147 (18), 134 (20), 128 (7), 120 (72), 110 (100), 92 (2
6), 65 (69). Elemental analysis (C ₁₄ H ₁₅ NO ₂ as S) Calculated: C, 64.36; H, 5.75 ; N, 5.36; S, 12.26. Found: C, 64.42; H, 5.78; N, 5.38; S, 12.08.

Product 3j: (Z) -4-phenyl-3-
Methyl phenylthio-2-butenoate Colorless liquid; boiling point 120 ° C. (0.2 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.41-6.86 (m, 10H), 5.74 (s, 1H, C = CH), 3.74 (s, 3H),
3.43 (s, 2H). ¹³ C NMR (CDCl ₃ ) δ ppm 166.5 (COOCH ₃ ), 160.6 (C = CH), 136.9, 136.2, 130.1,
129.4, 128.9, 128.7, 128.4, 126.7, 113.5 (C = CH), 51.
2, 43.0. IR (liquid film) 1705, 1582, 1437, 1174, 1025, 748, 694 cm ^-1 . GC-MS m / z (relative intensity) 284 (M ⁺ , 8), 252 (50), 174 (17), 115 (100), 91 (26), 6
9 (5).

Product 3j ': (E) -4-phenyl-3
-Methyl phenylthio-3-butenoate Colorless liquid; boiling point 120 ° C. (0.2 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.49-7.27 (m, 10H), 7.01 (s, 1H, C = CH), 3.69 (s, 3H),
3.45 (s, 2H). ¹³ C NMR (CDCl ₃ ) δ ppm 170.9 (COOCH ₃ ), 163.0 (C = CH), 136.1, 135.0, 132.0,
130.2, 129.2, 128.5, 128.3, 127.7, 127.6, 52.2, 37.
7. IR (liquid film) 1742, 1603, 1477, 1170, 748, 694 cm ^-1 . GC-MS m / z (relative intensity) 284 (M ⁺ , 41), 253 (4), 210 (40), 191 (11), 167 (25), 1
47 (24), 115 (100), 91 (34), 69 (20). Elemental analysis (a mixture of 3j and _{3j ') (C 17 H 16} O 2 as S) Calculated: C, 71.83; H, 5.63 ; S, 11.26. Found: C, 72.12; H, 6.12; S, 11.06.

Product 31: (Z) -3-phenylthio-
Methyl p-methoxycinnamate Colorless liquid; boiling point 120 ° C. (0.15 Torr). ¹ H NMR (CDCl ₃ ) δ ppm 7.16-6.60 (m, 9H), 6.07 (s, 1H, C = CH), 3.78 (s, 3H, O
_{CH 3), 3.68 (s,} 3H, OCH 3). ¹³ C NMR (CDCl ₃ ) δ ppm 166.2 (COOCH ₃ ), 159.8 (C = CH), 158.8, 133.5, 132.8,
130.6, 130.1, 128.4, 127.5, 115.4 (C = CH), 113.2, 55.
1, 51.4 (COOCH ₃ ). IR (KBr) 3004, 2950, 1702, 2840, 1707, 1605, 1582, 1508, 12
53, 1166, 1025, 832, 748, 690 cm- ¹ . GC-MS m / z (relative intensity) 300 (M ⁺ , 11), 269 (8), 240 (25), 191 (100), 151 (42),
135 (54), 117 (27), 108 (61), 89 (54), 65 (25), 59 (68). Elemental analysis (C ₁₇ H ₁₆ O ₃ as S) Calculated: C, 68.00; H, 5.33 ; S, 10.67. Found: C, 67.82; H, 5.36; S, 10.40.

Product 3m: (Z) -3-phenylthio-
Methyl p-fluorocinnamate mp 91-92 ° C. ¹ H NMR (CDCl ₃ ) δ ppm 7.15-7.03 (m, 7H), 6.81-6.75 (m, 2H), 6.06 (s, 1H, C =
CH), 3.81 (s, 3H , OCH 3). ¹³ C NMR (CDCl ₃ ) δ ppm 166.1 (COOCH ₃ ), 162.5 (d, J _CF = 249.1 Hz), 158.4 (C
= CH), 134.3 (d, ⁴ J _CF = 3.3 Hz), 134.0, 132.1, 130.5
(d, ³ J _CF = 8.3 Hz), 128.5, 127.9, 115.9 (C = CH), 11
4.9 (d, ² J _CF = 21.8 Hz), 51.5 (COOCH ₃ ). IR (KBr) 1709, 1603, 1506, 1170, 1023, 833 cm- ¹ . GC-MS m / z (relative intensity) 288 (M ⁺ , 14), 257 (62), 229 (62), 179 (19), 165 (10),
139 (41), 120 (28), 109 (51), 59 (100). Elemental analysis (C ₁₆ H ₁₃ FO ₂ as S) Calculated: C, 66.65; H, 4.51 ; S, 11.11. Found: C, 66.23; H, 4.08; S, 10.84.

Examples 14 to 25 Table 2 shows the results of a reaction under the same conditions as in Example 1 using toluene as a solvent and various catalysts.

[0035]

[Table 2]

[0036]

According to the method of the present invention, it is possible to safely and efficiently synthesize a beta-arylthioacrylic acid ester derivative useful for synthesizing medicines and agricultural chemicals from easily available thiocarbonate and acetylene. It can be easily isolated and purified. Therefore, the present invention has a great effect industrially.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Mizumo Hana 1-1-1, Higashi, Tsukuba-shi, Ibaraki Pref. BA48 TA04 TB72 4H039 CA61 CA65 CF20 4H049 VN01 VP01 VQ49 VR23 VR41 VU33

Claims (9)

[Claims] 1. A compound of the formula (II) R ¹ C≡CH (II) wherein R ¹ is an alkyl group which may have a substituent, An optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted aryl group, An aralkyl group which may be substituted, a heterocyclic group which may have a substituent or a silyl group which may have a substituent.) Is represented by the general formula (III): ArSCOOR ² (III) (wherein, R ² is an alkyl group which may have a substituent,
An aryl group which may have a substituent or an aralkyl group which may have a substituent is represented, and Ar represents an aryl group which may have a substituent. Wherein R ¹ (ArS) C ＝ CHCOOR ² (I) (wherein R ¹ , R ² and Ar are the same as those described above). )). 2. The method according to claim 1, wherein the metal complex catalyst is a transition metal complex catalyst. 3. The method according to claim 2, wherein the transition metal is palladium or rhodium. 4. The method according to claim 2, wherein the transition metal complex catalyst is a low valent complex catalyst. 5. The production method according to claim 2, wherein the transition metal complex catalyst is a palladium zero-valent complex having a tertiary phosphine or a tertiary phosphite as a ligand. 6. The method according to claim 2, wherein the transition metal complex catalyst is a monovalent rhodium complex having a tertiary phosphine or a tertiary phosphite as a ligand. 7. The production method according to claim 2, wherein the transition metal complex catalyst is a precursor complex that can be easily converted to a low-valent complex in the reaction system. 8. A transition metal complex catalyst comprising a combination of a tertiary phosphine or a tertiary phosphite and / or a tertiary phosphine and / or a tertiary phosphite and a transition metal complex not containing a tertiary phosphine or a tertiary phosphite as a ligand. The production method according to claim 2 or 3, which is a low-valent complex having the formed tertiary phosphine and / or tertiary phosphite as a ligand. 9. formula ^{_{(I ') R 0 1 (}} ArS) C = CHCOOR 2 (I') ( _{wherein, R} ^{0 1} is an alkyl group optionally having a substituent, have a substituent An optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkenyl group, an optionally substituted aralkyl group, A heterocyclic group which may be
A silyl group or a substituted aryl group which may have a substituent, wherein R ² is an alkyl group which may have a substituent,
An aryl group which may have a substituent or an aralkyl group which may have a substituent is represented, and Ar represents an aryl group which may have a substituent. ) A beta aryl thioacrylate derivative represented by the formula: