KR20100078939A - Novel allenyl sulfide compounds and synthesis of them - Google Patents

Abstract

PURPOSE: An allenyl sulfide derivative and a manufacturing method thereof are provided to obtain the allenyl sulfide derivative with the high yield over 70% with a simple reaction. CONSTITUTION: An allenyl sulfide derivative is marked with chemical formula 1. In the chemical formula 1, R1 and R2 are a C1~C10 alkyl group, or a C6~C12 aryl group, respectively. The R1 and the R2 are capable of forming a 3-8-membered ring by being bonded with a C2~C7 alkylene group. R3 is either the C1~C10 alkyl group, or the C6~C12 aryl group. R4 is hydrogen or the C1~C10 alkyl group.

Description

Novel allenyl sulfide compounds and synthesis of them

The present invention relates to a novel allenyl sulfide derivative using an organic sulfur-indium complex and a method for preparing the same. More particularly, the present invention relates to a new type of reaction reagent, indium, which is used to increase the nucleophilicity of thiol. The present invention relates to a novel allenyl sulfide derivative represented by the following Chemical Formula 1 prepared by cross-coupling tri (organothiolate) and tertiary propazyl acetate and a method of preparing the same.

[Formula 1]

[In Formula 1,

R ¹ and R ² are independently of each other (C1-C10) alkyl or (C6-C12) aryl, or R ¹ and R ² are linked with (C2-C7) alkylene to form a 3-8 membered ring. Can be;

R ³ is (C1-C10) alkyl or (C6-C12) aryl;

R ⁴ is hydrogen or (C 1 -C 10) alkyl;

Alkyl or aryl of R ¹ , R ² , R ³ and R ⁴ may be selected from the group consisting of (C1-C10) alkyl, (C1-C10) alkoxy, halogen, (C6-C12) aryl and acetyl. May be further substituted.]

Since allene compounds are useful as raw materials for preparing various materials, they are of great interest for the synthesis of allenyl sulfide compounds having various substituents introduced therein.

In general, known synthesis methods of allenyl sulfide compounds include reduction reactions of allenyl sulfoxide compounds (Cookson, R. Chem. Commun. 1978, 822, Mattay, J. Synthesis 1991, 1, 11), lithium alkyl thiols Reactions with late derivatives, phosphine oxides and aldehydes (Huang, X. Tetrahedron Letters 2003, 44, 5913), cross-coupling reactions with propazyl halide derivatives and metal catalysts (Kakiuchi, K. Eur. J. Org. Chem. 2004, 504).

 These reactions are difficult to prepare reagents and have limitations on the introduction of various substituents.

Therefore, there is a need for a method for producing an allenyl sulfide compound having a simpler manufacturing method and various substituents introduced using an organometallic compound having a wide selection of functional groups.

An object of the present invention is to provide a novel allenyl sulfide derivative.

Another object of the present invention is to provide a novel method for preparing allenyl sulfide derivatives by cross-coupling indium tri (organothiolate) and tertiary propazyl acetate.

The present invention relates to a novel allenyl sulfide derivative using an organic sulfur-indium complex and a method for preparing the same. More particularly, the present invention relates to a new type of reaction reagent, indium, which is used to increase the nucleophilicity of thiol. It relates to a novel allenyl sulfide derivative represented by the following formula (1) prepared by tri-organothiolate and tertiary propazyl acetate under a palladium catalyst and a method for preparing the same.

[Formula 1]

[In Formula 1,

R ¹ and R ² are independently of each other (C1-C10) alkyl or (C6-C12) aryl, or R ¹ and R ² are linked with (C2-C7) alkylene to form a 3-8 membered ring. Can be;

R ³ is (C1-C10) alkyl or (C6-C12) aryl;

R ⁴ is hydrogen or (C 1 -C 10) alkyl;

Alkyl or aryl of R ¹ , R ² , R ³ and R ⁴ may be selected from the group consisting of (C1-C10) alkyl, (C1-C10) alkoxy, halogen, (C6-C12) aryl and acetyl. May be further substituted.]

"Alkyl" in the present invention includes a straight or pulverized saturated carbon chain having 1 to 10 carbon atoms.

Specifically, R ¹ and R ² are independently of each other methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n -Heptyl, n-octyl, n-nonyl, 2-ethylhexyl, decyl, trifluoromethyl, benzyl, phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-bromophenyl, 3- Bromophenyl, 4-bromophenyl, 2-acetylphenyl, 3-acetylphenyl, 4-acetylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl or biphenyl or C5 alkylene Can be linked to form a six-membered ring; R ³ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl 2-ethylhexyl, decyl, trifluoromethyl, benzyl, phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2- acetylphenyl, 3-acetylphenyl, 4-acetylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl or biphenyl; R ⁴ is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, n -Nonyl, 2-ethylhexyl, decyl, trifluoromethyl or benzyl.

More specifically, the allenyl sulfide derivative of Chemical Formula 1 is R ¹ is phenyl, 3-acetylphenyl or 4-bromophenyl; R ² is methyl; R ¹ and R ² may be linked to pentylene (—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —) to form a cyclohexyl which is a 6 membered ring; R ³ is n-propyl, isopropyl, t-butyl, phenyl, 4-methylphenyl or 4-methoxyphenyl; R ⁴ is a hydrogen atom, methyl or t-butyl.

 Specific examples of the allenyl sulfide derivative represented by Formula 1 according to the present invention are as follows:

(3-phenyl-1,2-butadienyl) (4-methylphenyl) sulfide,

(3-phenyl-1,2-butadienyl) (4-methoxyphenyl) sulfide,

(3-phenyl-1,2-butadienyl) (phenyl) sulfide,

(3-phenyl-1,2-butadienyl) (isopropyl) sulfide,

(3-phenyl-1,2-butadienyl) (n-propyl) sulfide,

(3-phenyl-1,2-butadienyl) (tert-butyl) sulfide,

(3- (4-bromophenyl) -1,2-butadienyl) (4-methoxyphenyl) sulfide,

(3- (4-bromophenyl) -1,2-butadienyl) (isopropyl) sulfide,

(3- (4-bromophenyl) -1,2-butadienyl) (phenyl) sulfide,

(2-cyclohexylidenevinyl) (4-methylphenyl) sulfide,

(2-cyclohelylidenevinyl) (4-methoxyphenyl) sulfide,

(2-cyclohexylidenevinyl) (phenyl) sulfide,

(2-cyclohexylidenevinyl) (isopropyl) sulfide,

3- (4- (phenylthio) buta-2,3-dien-2-yl) phenyl acetate,

3- (4- (tert-butylthio) buta-2,3-dien-2-yl) phenyl acetate,

(4-methoxyphenyl) (4-phenylpenta-2,3-dien-2-yl) sulfide,

(Isopropyl) (4-phenylpenta-2,3-dien-2-yl) sulfide,

(4-methoxyphenyl) 2-phenylocta-2,3-dien-4-yl) sulfide,

(2-phenylocta-2,3-dien-4-yl) (n-propyl) sulfide,

(2-phenylocta-2,3-dien-4-yl) (phenyl) sulfide.

In addition, the present invention includes a method for preparing an allenyl sulfide derivative represented by Chemical Formula 1, and more specifically, in the presence of a palladium catalyst and a phosphine ligand, in order to increase the nucleophilicity of a thiol A novel allenyl sulfide derivative represented by Chemical Formula 1 is prepared by cross-coupling a reaction reagent, indium tri (organothiolate) (Formula 3), with tertiary propazyl acetate (Formula 2). One).

Scheme 1

[In Reaction Scheme 1, R ¹ and R ² are independently of each other (C1-C10) alkyl or (C6-C12) aryl, or R ¹ and R ² are connected to (C2-C7) alkylene and 3 to 8 Can form a ring of circles; R ³ is (C1-C10) alkyl or (C6-C12) aryl; R ⁴ is hydrogen or (C 1 -C 10) alkyl; Alkyl or aryl of R ¹ , R ² , R ³ and R ⁴ may be selected from the group consisting of (C1-C10) alkyl, (C1-C10) alkoxy, halogen, (C6-C12) aryl and acetyl. May be further substituted.]

As the reaction catalyst used in the preparation method of the present invention, a palladium catalyst is used, but the palladium catalyst is Pd ₂ dba ₃ CHCl ₃ , Pd (OAc) ₂ , (dppf) PdCl ₂ , Pd (PPh ₃ ) ₄ , (PPh ₃ ) ₂ PdCl ₂ , (DPEphos) PdCl ₂ and PdCl ₂ are selected and used, preferably Pd ₂ dba ₃ CHCl ₃ is used. Phosphine ligands are used as reaction ligands, but phosphine ligands are bis (2-diphenylphosphinophenyl) ether [DPEphos; Bis (2-diphenylphosphinophenyl) ether], 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene [Xantphos; 4,5-Bis (diphenylphosphino) -9,9-dimethylxanthene], cyclohexyl diphenyl phosphine [(Biph) PCy ₂ ], 1,1'-bis (diphenylphosphino) ferrocene [DPPF; 1,1'-Bis (diphenylphosohino) ferrocene], 1,2-bis (diphenylphosphino) ether [DPPE; 1,2-Bis (diphenylphosohino) ether] or 1,3-bis (diphenylphosphino) propane [DPPP; 1,3-Bis (diphenylphosohino) propane] can be selected from the group consisting of, DPEphos is recommended as the optimal ligand to increase the activity of palladium. As the reaction solvent, a conventional organic solvent such as dimethylformamide (DMF) or tetrahydrofuran (THF) is used, and preferably, the reaction is performed using dimethylformamide (DMF). The reaction temperature is maintained at 25 ° C. to the reflux temperature range of the solvent used, preferably from 25 ° C. to 100 ° C. Particular preference is given to maintaining 25 ° C. to 100 ° C. under dimethylformamide (DMF) solvent. The reaction time may vary depending on the reactants, the type of solvent, and the amount of the solvent, and then complete the reaction after confirming that all the starting materials are consumed through TLC. After the reaction is completed, the solvent may be distilled off under reduced pressure through the extraction process, and then the target product may be separated and purified through conventional methods such as column chromatography.

The allenyl sulfide derivative of the present invention is a novel substance having various substituents introduced therein, which is useful as a raw material for preparing various substances, and cross-couples reaction of indium triorgano thioleate with tertiary propazyl acetate. To be manufactured. The indium tri (organothiolate) is a new type of reaction reagent for increasing the nucleophilicity of thiol, and the reaction is simple compared to the conventional method for preparing allenyl sulfide derivatives, and 70% Allenyl sulfide derivatives can be obtained with the above high yield.

The present invention as described above will be described in more detail through the following examples, the following examples are intended to help the understanding of the present invention is not limited to the scope of the present invention.

[ Example ]

Example 1 Preparation of (3-phenyl-1,2-butadienyl) (4-methylphenyl) sulfide [(3-phenyl-1,2-butadienyl) (4-methylphenyl) sulfide]

Under nitrogen atmosphere, Pd ₂ dba ₃ CHCl ₃ (6.21 mg, 0.006 mmol) and DPEphos (12.9 mg, 0.024 mmol) were stirred for 10 minutes at room temperature using DMF (0.6 mL), followed by 2-phenylbuta-3-yne-. 2-yl acetate (56.5 mg, 0.3 mmol) is dissolved in DMF (0.2 mL) and added and stirred for 1 minute. To this solution, In (Sp-Tol) ₃ (48.4 mg, 0.1 mmol) is added dissolved in DMF (0.4 mL). The reaction was stirred at 25 ° C. for 5 hours, and 5% aqueous hydrochloric acid solution (1 mL) was added to terminate the reaction. The mixture was extracted with Et ₂ O (15 mL × 3) and washed with saturated NH ₄ Cl (10 mL) and saturated aqueous NaCl solution (10 mL). The extracted organics were dried over anhydrous MgSO ₄ and filtered. The solvent was removed and the residue was separated by column chromatography to give 57 mg (76%) of the desired product.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.39-7.21 (m, 7H), 7.10 (d, J = 7.7 Hz, 2H), 6.23 (q, J = 2.6 Hz, 1H), 2.31 (s, 3H ), 2.10 (d, J = 2.8 Hz, 3H).

Example 2 Preparation of (3-phenyl-1,2-butadienyl) (4-methoxyphenyl) sulfide [(3-phenyl-1,2-butadienyl) (4-methoxyphenyl) sulfide]

It was prepared in the same manner as in Example 1. However, In (Sp-methoxyphenyl) ₃ (53.2 mg, 0.1 mmol) was used instead of In (Sp-Tol) ₃ to obtain the desired product (70 mg, 86%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.39 (d, J = 8.9 Hz, 2H), 7.36-7.29 (m, 4H), 7.24-7.20 (m, 1H), 6.82 (d, J = 8.9 Hz , 2H), 6.19 (d, J = 2.7 Hz, 1H), 3.77 (s, 3H), 2.05 (d, J = 2.7 Hz, 3H).

Example 3 Preparation of (3-phenyl-1,2-butadienyl) (phenyl) sulfide [(3-phenyl-1,2-butadienyl) (phenyl) sulfide]

It was prepared in the same manner as in Example 1. However, In (SPh) ₃ (44.2 mg, 0.1 mmol) was used instead of In (Sp-Tol) ₃ to obtain the desired product (59 mg, 83%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.44-7.18 (m, 10H), 6.26 (q, J = 2.6 Hz, 1H), 2.11 (d, J = 2.6 Hz, 3H)

Example 4 Preparation of (3-phenyl-1,2-butadienyl) (isopropyl) sulfide [(3-phenyl-1,2-butadienyl) (isopropyl) sulfide]

It was prepared in the same manner as in Example 1. However, In (S-iso-Pr) ₃ (34.1 mg, 0.1 mmol) was used instead of In (Sp-Tol) ₃ to obtain the desired product (54 mg, 88%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.42 (d, J = 7.6 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H), 7.22 (t, J = 7.3 Hz, 1H), 6.09 ( q, J = 2.8 Hz, 1H), 3.10-3.00 (m, 1H), 2.16 (d, J = 2.8 Hz, 3H), 1.34 (d, J = 6.7 Hz, 3H), 1.28 (d, J = 6.7 Hz, 3H)

Example 5 Preparation of (3-phenyl-1,2-butadienyl) (n-propyl) sulfide [(3-phenyl-1,2-butadienyl) (n-propyl) sulfide]

It was prepared in the same manner as in Example 1. However, In (Sn-Pr) ₃ (34.1 mg, 0.1 mmol) was used instead of In (Sp-Tol) ₃ to obtain the desired product (55 mg, 90%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.43 (d, J = 7.6 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H), 7.2 (t, J = 7.3 Hz, 1H), 6.09 ( q, J = 2.8 Hz, 1H), 2.64-2.52 (m, 2H), 2.16 (d, J = 2.8 Hz, 3H), 1.67-1.57 (m, 2H), 0.93 (t, J = 7.3 Hz, 3H )

Example 6 Preparation of (3-phenyl-1,2-butadienyl) (tert-butyl) sulfide [(3-phenyl-1,2-butadienyl) (tert-butyl) sulfide]

It was prepared in the same manner as in Example 1. However, In (S-tert-Bu) ₃ (38.2 mg, 0.1 mmol) was used instead of In (Sp-Tol) ₃ to obtain the desired product (56 mg, 86%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.42-7.20 (m, 5H), 6.13 (d, J = 2.6 Hz, 1H), 2.15 (d, J = 2.6 Hz, 3H), 1.41 (s, 9H )

[Example 7] (3- (4-bromophenyl) -1,2-butadienyl) (4-methoxyphenyl) sulfide [(3- (4-bromophenyl) -1,2-butadienyl) ( 4-methoxyphenyl) sulfide]

It was prepared in the same manner as in Example 1. 2- (4-bromophenyl) buta-3-yn-2-yl acetate (80.1 mg, 0.3 mmol), In (Sp-Tol) ₃ instead of 2-phenylbuta-3-yn-2-yl acetate Instead, In (Sp-methoxyphenyl) ₃ (53.2 mg, 0.1 mmol) was used to obtain the desired product (82.6 mg, 80%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.41 (d, J = 8.7 Hz, 2H), 7.37 (d, J = 8.7 Hz, 2H), 7.18 (d, J = 8.6 Hz, 2H), 6.81 ( d, J = 8.6 Hz, 2H), 6.19 (q, J = 2.6 Hz, 1H), 3.77 (s, 3H), 2.00 (d, J = 2.6 Hz, 3H)

Example 8 (3- (4-bromophenyl) -1,2-butadienyl) (isopropyl) sulfide [(3- (4-bromophenyl) -1,2-butadienyl) (isopropyl) sulfide Manufacture of

It was prepared in the same manner as in Example 1. 2- (4-bromophenyl) buta-3-yn-2-yl acetate (80.1 mg, 0.3 mmol), In (Sp-Tol) ₃ instead of 2-phenylbuta-3-yn-2-yl acetate Instead, In (S-iso-Pr) ₃ (34.1 mg, 0.1 mmol) was used to give the desired product (74.6 mg, 88%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.45 (d, J = 8.6 Hz, 2H), 7.28 (d, J = 8.6 Hz, 2H), 6.10 (q, J = 2.8 Hz, 1H), 3.06- 3.0 (m, 1H), 2.13 (d, J = 2.8 Hz, 3H), 1.34 (d, J = 6.7 Hz, 3H), 1.27 (d, J = 6.7 Hz, 3H)

Example 9 (3- (4-bromophenyl) -1,2-butadienyl) (phenyl) sulfide [(3- (4-bromophenyl) -1,2-butadienyl) (phenyl) sulfide] Manufacture

It was prepared in the same manner as in Example 1. However, 2- (4-bromophenyl) buta-3-yn-2-yl acetate (80.1 mg, 0.3 mmol), In (Sp-Tol) instead of 2-phenylbuta-3-yn-2-yl acetate ) ₃ instead of in (SPh) ₃ (using the 44.2 mg, 0.1 mmol) to give the desired product (77 mg, 81%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.44 (d, J = 8.6 Hz, 2H), 7.32-7.25 (m, 5H), 7.22 (d, J = 8.6 Hz, 2H), 6.26 (q, J = 2.6 Hz, 1H), 2.07 (s, 3H)

Example 10 (3- (4- (phenylthio) buta-2,3-dien-2-yl) phenyl) acetate [3- (4- (phenylthio) buta-2,3-dien-2 -yl) phenyl acetate]

It was prepared in the same manner as in Example 1. Instead of 2-phenylbuta-3-yn-2-yl acetate, instead of 2- (3-acetylphenyl) buta-3-yn-2-yl acetate (73.9 mg, 0.3 mmol), In (Sp-Tol) ₃ In (SPh) ₃ (44.2 mg, 0.1 mmol) was used to give the desired product (69.2 mg, 78%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.43 (d, J = 7.6 Hz, 2H), 7.34-7.19 (m, 5H), 7.07 (t, J = 1.7 Hz, 1H), 6.96 (d, J = 8.2 Hz, 1H), 6.28 (q, J = 2.6 Hz, 1H), 2.30 (s, 3H), 2.07 (s, 3H)

Example 11 3- (4- (tert-butylthio) buta-2,3-dien-2-yl) phenyl acetate [3- (4- (tert-butylthio) buta-2,3-dien -2-yl) phenyl acetate]

It was prepared in the same manner as in Example 1. Instead of 2-phenylbuta-3-yn-2-yl acetate, instead of 2- (3-acetylphenyl) buta-3-yn-2-yl acetate (73.9 mg, 0.3 mmol), In (Sp-Tol) ₃ In (S-tert-Bu) ₃ (38.2 mg, 0.1 mmol) was used to give the desired product (64 mg, 75%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.33 (t, J = 7.8 Hz, 1H), 7.27 (d, J = 6.8 Hz, 1H), 7.10 (t, J = 1.9 Hz, 1H), 6.95 ( d, J = 7.8 Hz, 1H), 6.14 (q, J = 2.6 Hz, 1H), 2.29 (s, 3H), 2.13 (d, J = 2.6 Hz, 3H), 1.40 (s, 9H).

Example 12 Preparation of (2-cyclohexylidenevinyl) (4-methylphenyl) sulfide [(2-cyclohexylidenevinyl) (4-methylphenyl) sulfide]

Under nitrogen atmosphere, Pd ₂ dba ₃ CHCl ₃ (6.21 mg, 0.006 mmol) and DPEphos (12.9 mg, 0.024 mmol) were stirred for 10 minutes at room temperature using DMF (0.6 mL), followed by 1-ethynylcyclohexyl acetate ( 49.9 mg, 0.3 mmol) is added dissolved in DMF (0.2 mL) and stirred for 1 minute. To this solution, In (Sp-Tol) ₃ (48.4 mg, 0.1 mmol) is added dissolved in DMF (0.4 mL). The reaction was stirred at 100 ° C. for 1 hour, and 5% aqueous hydrochloric acid solution (1 mL) was added to terminate the reaction. The mixture was extracted with Et ₂ O (15 mL × 3) and washed with saturated NH ₄ Cl (10 mL) and saturated aqueous NaCl solution (10 mL). The extracted organics were dried over anhydrous MgSO ₄ and filtered. The solvent was removed and then separated by column chromatography to give 57.6 mg (83%) of the desired product.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.29 (d, J = 8.0 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 5.77-5.75 (m, 1H), 2.32 (s, 3H ), 2.13-2.10 (m, 4H), 1.57-1.48 (m, 6H)

Example 13 Preparation of (2-cyclohexylidenevinyl) (4-methoxyphenyl) sulfide [(2-cyclohexylidenevinyl) (4-methoxyphenyl) sulfide]

It was prepared in the same manner as in Example 12. However, In (Sp-methoxyphenyl) ₃ (53.2 mg, 0.1 mmol) was used instead of In (Sp-Tol) ₃ to obtain the desired product (59 mg, 80%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.36 (d, J = 8.8 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 5.74-5.72 (m, 1H), 3.80 (s, 3H ), 2.09-2.06 (m, 4H), 1.57-1.51 (m, 2H), 1.48-1.41 (m, 4H)

Example 14 Preparation of (2-cyclohexylidenevinyl) (phenyl) sulfide [(2-cyclohexylidenevinyl) (phenyl) sulfide]

It was prepared in the same manner as in Example 12. However, In (SPh) ₃ (53.2 mg, 0.1 mmol) was used instead of In (Sp-Tol) ₃ to obtain the desired product (54.5 mg, 84%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.39 (d, J = 7.8 Hz, 2H), 7.30 (t, J = 7.7 Hz, 2H), 7.20 (t, J = 7.3 Hz, 1H), 5.80- 5.78 (m, 1H), 2.17-2.10 (m, 4H), 1.62-1.46 (m, 6H)

Example 15 Preparation of (2-cyclohexylidenevinyl) (isopropyl) sulfide [(2-cyclohexylidenevinyl) (isopropyl) sulfide]

It was prepared in the same manner as in Example 12. However, In (S-iso-Pr) ₃ (34.1 mg, 0.1 mmol) was used instead of In (Sp-Tol) ₃ to obtain the desired product (45.1 mg, 82%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 5.62-5.60 (m, 1H), 3.08-2.97 (m, 1H), 2.19-2.14 (m, 4H), 1.65-1.52 (m, 6H), 1.31 ( s, 3H), 1.30 (s, 3H)

Example 16 (4-methoxyphenyl) (4-phenylpenta-2,3-dien-2-yl) sulfide [(4-methoxyphenyl) (4-phenylpenta-2,3-dien-2-yl ) sulfide]

It was prepared in the same manner as in Example 12. 2-phenylpenta-3-yn-2-yl acetate (60.7 mg, 0.3 mmol) instead of 1-ethynylcyclohexyl acetate, In (Sp-methoxyphenyl) ₃ (53.2 mg, instead of In (Sp-Tol) ₃ 0.1 mmol) was used to give the desired product (70 mg, 83%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.35 (d, J = 8.8 Hz, 2H), 7.30-7.26 (m, 4H), 7.20-7.17 (m, 1H), 6.75 (d, J = 8.8 Hz , 2H), 3.73 (s, 3H), 2.01 (s, 3H), 1.92 (s, 3H)

Example 17 Preparation of (Isopropyl) (4-phenylpenta-2,3-dien-2-yl) sulfide [(isopropyl) (4-phenylpenta-2,3-dien-2-yl) sulfide]

It was prepared in the same manner as in Example 12. 2-phenylpenta-3-yn-2-yl acetate (60.7 mg, 0.3 mmol) instead of 1-ethynylcyclohexyl acetate, In (S-iso-Pr) ₃ (34.1 instead of In (Sp-Tol) ₃ mg, 0.1 mmol) was used to give the desired product (54.4 mg, 84%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.42 (d, J = 7.5 Hz, 2H), 7.33 (t, J = 7.7 Hz, 2H), 7.21 (t, J = 7.3 Hz, 1H), 3.37- 3.33 (m, 1H), 2.25 (s, 3H), 1.96 (s, 3H), 1.34 (d, J = 6.8 Hz, 6H)

Example 18 (4-methoxyphenyl) (2-phenylocta-2,3-dien-4-yl) sulfide [(4-methoxyphenyl) (2-phenylocta-2,3-dien-4-yl ) sulfide]

It was prepared in the same manner as in Example 12. 2-phenylocta-3-yn-2-yl acetate (73.3 mg, 0.3 mmol) instead of 1-ethynylcyclohexyl acetate, In (Sp-methoxyphenyl) ₃ (53.2 mg, instead of In (Sp-Tol) ₃ 0.1 mmol) was used to give the desired product (69.7 mg, 72%).

¹ H NMR (400 MHz, DMSO): δ 7.35-7.20 (m, 7H), 6.86 (d, J = 8.7 Hz, 2H), 3.71 (s, 3H), 2.22 (td, J = 7.4, 2.2 Hz, 2H), 1.92 (s, 3H), 1.51-1.44 (m, 2H), 1.36-1.28 (m, 2H), 0.82 (t, J = 7.3 Hz, 3H)

Example 19 Preparation of (2-phenylocta-2,3-dien-4-yl) (phenyl) sulfide [(2-phenylocta-2,3-dien-4-yl) (phenyl) sulfide]

It was prepared in the same manner as in Example 12. 2-phenylocta-3-yn-2-yl acetate (73.3 mg, 0.3 mmol) instead of 1-ethynylcyclohexyl acetate, In (SPh) ₃ (44.2 mg, 0.1 mmol instead of In (Sp-Tol) ₃ ) To give the desired product (72 mg, 82%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.41-7.18 (m, 10H), 2.33-2.28 (m, 2H), 1.99 (s, 3H), 1.59-1.50 (m, 2H), 1.43-1.31 ( m, 2H), 0.87 (t, J = 7.4 Hz, 3H)

Example 20 (2-phenylocta-2,3-dien-4-yl) (n-propyl) sulfide [(2-phenylocta-2,3-dien-4-yl) (n-propyl) sulfide Manufacture of

It was prepared in the same manner as in Example 12. However, instead of 1-cyclohexyl-2-phenyl acetate ethynyl-3-octanoyl-2-yl acetate in (73.3 mg, 0.3 mmol), In (Sp-Tol) 3 instead of _{In (Sn-Pr) 3 (} 34.1 mg, 0.1 mmol) was used to give the desired product (73.3 mg, 81%).

¹ H NMR (400 MHz, DMSO): δ 7.40-7.34 (m, 4H), 7.26-7.22 (m, 1H), 2.47 (t, d, J = 7.2, 2.2 Hz, 2H), 2.21 (t, d , J = 7.3, 2.8 Hz, 2H), 2.11 (s, 3H), 1.52-1.43 (m, 4H), 1.38-1.31 (m, 2H), 0.85 (t, J = 7.2 Hz, 3H), 0.82 ( t, J = 7.3 Hz, 3H).

Claims (7)

Allenyl sulfide derivative represented by the following formula (1): [Formula 1]

[In Formula 1, R ¹ and R ² are independently of each other (C1-C10) alkyl or (C6-C12) aryl, or R ¹ and R ² are linked with (C2-C7) alkylene to form a 3-8 membered ring. Can be; R ³ is (C1-C10) alkyl or (C6-C12) aryl; R ⁴ is hydrogen or (C 1 -C 10) alkyl; Alkyl or aryl of R ¹ , R ² , R ³ and R ⁴ may be selected from the group consisting of (C1-C10) alkyl, (C1-C10) alkoxy, halogen, (C6-C12) aryl and acetyl. May be further substituted.] The method of claim 1, R ¹ and R ² are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, 2-ethylhexyl, decyl, trifluoromethyl, benzyl, phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-bromophenyl, 3-bromophenyl , 4-bromophenyl, 2-acetylphenyl, 3-acetylphenyl, 4-acetylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl or biphenyl, or linked by C5 alkylene Can form a six-membered ring; R ³ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl 2-ethylhexyl, decyl, trifluoromethyl, benzyl, phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-acetylphenyl, 3-acetylphenyl, 4-acetylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl or biphenyl; R ⁴ is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, n An allylyl sulfide derivative, characterized in that it is nonyl, 2-ethylhexyl, decyl, trifluoromethyl or benzyl. 3. The method of claim 2, Allenyl sulfide derivatives selected from the following compounds. (3-phenyl-1,2-butadienyl) (4-methylphenyl) sulfide, (3-phenyl-1,2-butadienyl) (4-methoxyphenyl) sulfide, (3-phenyl-1,2-butadienyl) (phenyl) sulfide, (3-phenyl-1,2-butadienyl) (isopropyl) sulfide, (3-phenyl-1,2-butadienyl) (n-propyl) sulfide, (3-phenyl-1,2-butadienyl) (tert-butyl) sulfide, (3- (4-bromophenyl) -1,2-butadienyl) (4-methoxyphenyl) sulfide, (3- (4-bromophenyl) -1,2-butadienyl) (isopropyl) sulfide, (3- (4-bromophenyl) -1,2-butadienyl) (phenyl) sulfide, (2-cyclohexylidenevinyl) (4-methylphenyl) sulfide, (2-cyclohelylidenevinyl) (4-methoxyphenyl) sulfide, (2-cyclohexylidenevinyl) (phenyl) sulfide, (2-cyclohexylidenevinyl) (isopropyl) sulfide, 3- (4- (phenylthio) buta-2,3-dien-2-yl) phenyl acetate, 3- (4- (tert-butylthio) buta-2,3-dien-2-yl) phenyl acetate, (4-methoxyphenyl) (4-phenylpenta-2,3-dien-2-yl) sulfide, (Isopropyl) (4-phenylpenta-2,3-dien-2-yl) sulfide, (4-methoxyphenyl) 2-phenylocta-2,3-dien-4-yl) sulfide, (2-phenylocta-2,3-dien-4-yl) (n-propyl) sulfide, (2-phenylocta-2,3-dien-4-yl) (phenyl) sulfide. In the presence of a palladium catalyst and a phosphine ligand, a propargyl acetate derivative represented by the following formula (2) and an indium tri (organothiolate) represented by the formula (3) are cross-paired to react with the allenyl sulfide derivative represented by the formula (1). Method for producing an allenyl sulfide derivative represented by the formula (1) of claim 1 characterized in that for producing a. [Formula 1]

[Formula 2]

(3)

[In Formulas 1 to 3, R ¹ and R ² are independently of each other (C1-C10) alkyl or (C6-C12) aryl, or R ¹ and R ² are linked to (C2-C7) alkylene and are three-membered. To form an 8-membered ring; R ³ is (C1-C10) alkyl or (C6-C12) aryl; R ⁴ is hydrogen or (C 1 -C 10) alkyl; Alkyl or aryl of R ¹ , R ² , R ³ and R ⁴ may be selected from the group consisting of (C1-C10) alkyl, (C1-C10) alkoxy, halogen, (C6-C12) aryl and acetyl. May be further substituted.] The method of claim 4, wherein The palladium catalyst is Pd ₂ dba ₃ CHCl ₃ , Pd (OAc) ₂ , (dppf) PdCl ₂ , Pd (PPh ₃ ) ₄ , (PPh ₃ ) ₂ PdCl ₂ , (DPEphos) PdCl ₂ And PdCl _{2 The} production method characterized in that the group consisting of. The method of claim 4, wherein The phosphine ligands include bis (2-diphenylphosphinophenyl) ether, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, cyclohexyl diphenyl phosphine, 1,1'- A bis (diphenylphosphino) ferrocene, 1,2-bis (diphenylphosphino) ether and 1,3-bis (diphenylphosphino) propane. The method of claim 4, wherein The cross-coupling reaction is carried out at 25 ° C to 100 ° C in a solvent of dimethylformamide (DMF) or tetrahydrofuran (THF).