KR20150115997A - C5 sulfone compound, method for preparing the same, method for preparing crocetin dinitrile using the same, and use thereof - Google Patents

Abstract

The present invention relates to a novel C5 sulfone compound, a method for preparing same, and a method for producing a crocetin dinitrile compound and, more specifically, to a novel C5 sulfone compound having a hydrazone protective group, a method for preparing same, and a method for efficiently producing a crocetin dinitrile compound using the same. The novel sulfone compound in accordance with the present invention is stable and excellent in crystallization, and thus easy to be separated and purified, and to form E-structure in the case of forming a double bond. In addition, since sulfinic acid, which is a by-product of the bonding, is easily removed in the case of synthesizing crocetin dinitrile by using the sulfone compound, a pure final product can be efficiently obtained. The crocetin dinitrile compound in accordance with the present invention is a kind of carotene compounds, and has nitrile groups on both ends thereof, thus various types of reactivity are expectable. In addition, a nitrogen atom contained in both ends of the compound has high affinity with metals, thereby enabling self-assembly on the surface of the metal. Furthermore, the crocetin dinitrile compound can exhibit a general antioxidative activity of the carotene, and can be used as an electrical and electronic material such as an organic molecular wire or the like.

Description

C5 SULFONE COMPOUND, PROCESS FOR PRODUCING THE SAME, AND METHOD FOR PREPARING CROCETIN DINITRILE USING THE SAME, AND USE THEREOF,

The present invention relates to a C5 sulphone compound, a process for preparing the same, a process for producing crosetin dinitrile using the same and a use thereof, and more particularly to a novel C5 sulphone compound having a hydrazone protecting group, The present invention relates to a method for efficiently producing a cetin dinitrile compound.

The present invention relates to a C5 sulfone compound having a hydrazone protecting group, a process for producing the same, and a process for efficiently producing a crosetin dinitrile compound using the same.

The conventional method is as follows. (See prior art documents) by synthesizing a C10 unit compound in the manner of coupling a acetal compound using a Lewis acid as a catalyst (see prior art references), followed by a Wittig reaction to prepare a polyene chain. However, in this case, there is a problem that phosphine salts which are difficult to remove are produced as by-products and utilize BiHI salts which are difficult to purify, and Z-structure double bonds are mainly produced.

US 2006 / 0194973A1

 Frederico, D .; Donate, P. M .; Constantino, M. G .; Bronze, E. S .; Sairre, M. I., J. Org. Chem. 2003, 68, 9126-9128.  Kryshtal, G. V .; Zhdankina, G. M .; Ignat'evN.V .; Schulte, M .; Zlotin, S. G., Tetrahedron Lett. 2012, 53, 4971-4973.

A novel C5 sulphone compound having a hydrazone protecting group and a process for its preparation are provided. The present invention also provides a method for efficiently producing a crocetin dinitrile compound. The present invention also provides a crocetin dinitrile compound which contains nitrogen at both ends and is excellent in affinity for metals.

The present invention provides a C5 sulfone compound represented by the following formula (1).

[Chemical Formula 1]

The present invention also provides a process for preparing the C5 sulfone compound represented by the above formula (1).

The method comprises mixing a compound represented by the following formula (1a), a hydrazine and an amine compound.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

The above formulas (1b) to (1c) include a hydroxymethyl group or an ester group instead of a formyl group. The reactivity of these regioisomeric conjugated hydroxymethyl-sulfone and conjugated sulfone-ester anions is poor. That is, it is advantageous to use formula (Ia) containing a formyl group because the yield of hydroxymethyl-sulfone is low due to the elimination of the hydroxyl group in the dianionic form and the regioselectivity is poor in allylation of the sulfone-ester .

In the above method, the compound represented by the formula (Ia) may be dissolved in an organic solvent to prepare a solution.

 The method comprises: preparing a solution by dissolving the compound of Formula 1a in an organic solvent; And adding and stirring hydrazine and an amine compound to the solution.

The method comprising: diluting with an organic solvent; Washing with water; On anhydrous Na ₂ SO ₄ Drying; Filtering; And concentrating under reduced pressure.

And further purifying by using a column chromatography.

The column chromatography may be silica gel flash column chromatography.

The organic solvent may be CH ₂ Cl ₂ .

The amine compound may be triethylamine.

The hydrazine may be 1,1-dimethylhydrazine.

When hydrazone is introduced into the compound of formula (Ia) using N, N-dimethylhydrazine, a very stable C ₅ compound of formula (1) can be prepared. This enables efficient synthesis of a new type of crocetin derivative-crocetin dinitrile.

The present invention also provides a crosetin dinitrile represented by the following general formula (3).

(3)

The crocetin dinitrile can be prepared by using the sulfonic compound represented by the formula (1).

The present invention also provides a process for preparing crocetin dinitrile represented by the following formula (3), which comprises reacting a C5 sulphone compound represented by the following formula (1) with a compound represented by the following formula (2).

[Chemical Formula 1]

(2)

(3)

The above step can be carried out by adding a basic substance in an organic solvent and reacting.

The basic material may be t- BuOK.

This step may comprise a step of preparing a compound represented by the formula (3a).

[Chemical Formula 3]

After step (a), the method may further include a step b of producing a compound represented by the following formula (3b) by adding a basic substance and a chlorine-providing substance to the organic solvent and a compound represented by the formula (3a).

(3b)

The basic substance may be at least one selected from the group consisting of t- BuOH and KOH.

As the material for providing the chlorine group, at least one selected from the group consisting of CCl ₄ and C ₂ Cl ₆ can be used.

After step (b), the method may further include the step of adding a basic substance to the organic solvent and a compound represented by the formula (3b) and reacting them to prepare a compound represented by the following formula (3c).

[Chemical Formula 3c]

The basic material may be KOMe.

After step (c), the method may further include a step d in which the compound represented by formula (3c) is mixed and reacted with an acetonitrile solution containing urea-hydrogen peroxide and phthalic anhydride.

The organic solvent may be DMF, CH ₂ Cl ₂ , C ₂ Cl ₆ , CHCl ₃ , Benzene, and cyclohexane.

Also, according to the present invention, it is possible to provide an organic molecular lead comprising the crocetin dinitrile represented by the general formula (3).

According to the present invention, it is possible to provide a compound for an electronic device comprising the crocetin dinitrile represented by the above formula (3).

 The sulfone compound according to the present invention is stable and easy to separate and purify because of its good crystallinity, and it is easy to prepare an E-structure when forming a double bond. Also, in the case of synthesizing crocetin dinitrile using the above sulfonic compound, it is easy to remove sulfinic acid, which is a byproduct of the coupling reaction, so that a pure final product can be efficiently obtained.

The crocetin dinitrile compound according to the present invention is a kind of carotene compound, and it can contain nitrile groups at both terminals and can be expected to have various reactivity. In addition, since the nitrogen atom contained in both ends has excellent affinity to metals, self-assembly is possible on the metal surface. In addition, it can exhibit the general antioxidant function of carotene and can be used as an electric and electronic material such as organic molecular lead.

Hereinafter, the present invention will be described more specifically by way of examples. It is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the present invention.

 Regioselective analysis of the sulfone compound (Formula 1)

Analysis of the chemoselectivity of C ₅ allylic sulfone 1 and allylic sulfide 11 with hydrazone protecting groups using hard (acetaldehyde) and soft (iodomethane) electrophilic reagents Respectively. Other metallic bases (NaHMDS or t-BuLi) also showed similar tendencies in the alkylation chemoselectivity of the C ₅ building block with the hydrazone protecting group, although there was some variation in the yield of the reaction product

[Reaction Scheme 1]

In the chemoselectivity of the alkylation with acetaldehyde, the difference between the allylic sulfone (1) and the allylic sulfide (11) was clearly different. The hard electrophilic reagent reacted at the [alpha] -carbon of the hydrazone at the ylrlic sulfide 11 to yield 12b (70% yield). On the other hand, allylic sulfone 1 produced 13a in a yield of 39% by gamma-alkylation of hydrazones. This indicates the anion-stabilizing effect of sulfone, which leads to? -Alkylation (? -T the hydrazone) but deactivates the anion's reactivity. On the other hand, as a soft electrophilic reagent, iodomethane reacted only at the soft gamma-carbon of hydrazones to produce 15a and 15b from allylic sulfone 1 and allylic sulfide 11, respectively. In this case, the? -Alkylated product 14a or 14b was not observed.

Preparation of crocetin dinitrile

A process for preparing crosetin dinitrile according to an embodiment of the present invention will be described with reference to the following Reaction Scheme 2. (Scheme 2 below is an embodiment of the present invention, and thus the scope of the present invention should not be limited.)

The use of the novel C ₅ allylic sulfone 1 with a hydrazone protecting group has been demonstrated in the synthesis of the novel crocetin derivative, crocetin dinitrile (Scheme 2). As expected from the regioselectivity analysis, the allylic sulfone (I) is converted to the C ₁₀ allylic chloride (III) in the base-promoted coupling ( t- BuOK in DMF) (2)) to give the trisulfone compound of formula 3b (72% yield).

(2)

[Chemical Formula 4]

(Yield: 56%; 3.5: 1 E / Z mixture at C8) with the Ramberg-Bücklund reaction (C ₂ Cl ₆ (in CH ₂ Cl ₂ ) as halogen source). Base-promoted elimination (KOMe, 80 占 폚) of the benzenesulfonyl group produced fully conjugated polyene 3c with hydrazone (yield of crude 88%). Methanol to easily prepare an analytical sample of formula (3c).

[Reaction Scheme 2]

Deprotection of hydrazones is not a simple task because the natural carotenoid polyenes under acid conditions are unstable. However, intramolecular oxidative dehydrogenation of ammonium oxides formed by oxidation of tertiary amines in dimethylhydrazone was induced to produce nitrile functional groups (parentheses in Reaction 2). Crocetin dinitrile (Formula 3) was obtained with a yield of 60% from the oxidation of hydrazone Formula 3c with mono perphthalic acid. Mono and perphthalic acid were generated from the in situ reaction of urea-hydrogen peroxide (UHP) and phthalic anhydride in acetonitrile. Crosetin dinitrile (3) was synthesized from a C ₅ building block having a hydrazone protecting group (Formula 1) at a total yield of 21% (Step 4).

In summary, according to the present invention, new types of C ₅ sulphone compounds can be provided. This allows sulfon-mediated synthesis of carotenoids with polar end groups. According to the present invention, it is possible to solve the regiochemical problem of a highly functionalized C ₅ building block and to efficiently synthesize crocetin dinitrile (Formula 3). Carotenoids having nitrile ends according to the present invention are more valuable because they have good affinity with various metal surfaces.

Hereinafter, the present invention will be described in more detail with reference to the following examples (production examples), but the scope of the present invention is not limited thereto.

^{The 1} H and ¹³ C NMR spectra were recorded on NMR spectroscopy at 400 MHz and 100 MHz, respectively, using TMS (tetramethylsilane) as an internal reference in deuterated chloroform (CDCl ₃ ). Solvents for extraction and chromatography were used as reagent grade. The column chromatography was carried out by using a mixture of EtOAc / hexane and a Still method using silica gel 60, 70-230 mesh ASTM (Merck). The reaction was carried out in a well-dried flask under argon atmosphere.

Production Example 1

Synthesis of [(E) -2-Methyl-4- (phenylsulfonyl) but-2-enal]

Methanol (100 mL) was added to ( E ) -4-chloro-2-methylbut-2-enal (11.10 g, 94.0 mmol) and p-TsOH (0.50 g, 2.80 mmol) was added to the stirred solution. The mixture was stirred for 1 hour at room temperature and NaSO ₂ Ph (15.40 g, 94.0 mmol) was added. The reaction mixture was stirred at room temperature for 12 hours, concentrated under reduced pressure and treated with 1 M hydrochloric acid (100 mL). The resulting mixture was stirred at room temperature for 1 hour, extracted with CH ₂ Cl ₂ , washed with ₁ M HCl and H ₂ O, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated under reduced pressure to give crude solid product. The solid product was purified by washing with ether to give compound (Ia).

Formula 1a Data: R _f = 0.07 (1: 4 EtOAc / hexane); mp 112-115 [deg.] C; ^{1 H NMR δ 1.48 (s,} 3H), 4.13 (d, J = 8.0 Hz, 2H), 6.45 (dt, J d = 1.6, J t = 8.0 Hz, 1H), 7.58 (t, J = 8.0 Hz, 2H), 7.70 (t, J = 7.6 Hz, 1H), 7.89 (d, J = 8.4 Hz, 2H), 9.46 (s, 1H) ppm; ¹³ C NMR? 9.2, 56.3, 128.2, 129.4, 134.3, 136.3, 138.3, 145.4, 193.5 ppm; IR (KBr) 3071, 2992, 2936, 2848, 1694, 1461, 1312, 1242, 1176, 1144, 1083, 1003, 919, 812, 746, 695, 578 cm ^-1 ; HRMS (CI ⁺ ) calcd for C ₁₁ H ₁₃ O ₃ S 225.0585, found 225.0578.

Production Example 2

Synthesis of formula (1)

[( E ) -1,1-Dimethyl-2 - (( E ) -2-methyl-4- (phenylsulfonyl) but-2-enylidene) hydrazine]

1,1-dimethylhydrazine (1.34 g, 13.93 mmol) and Et ₃ N (3.84 g, 13.93 mmol) were added to a stirred solution of the compound of formula 1a (2.84 g, 12.66 mmol) in CH ₂ Cl ₂ , 37.99 mmol). The reaction mixture was stirred at room temperature for 3 hours, diluted with CH ₂ Cl ₂ , washed with H ₂ O, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated under reduced pressure to give a crude product. This was purified by silica gel flash column chromatography to obtain a pale yellow solid (Formula 1, 2.50 g, 8.86 mmol) (yield: 70%).

Data of formula (1): mp 102-105 DEG C; _Rf = 0.52 (2: 3 EtOAc / hexane); ^{1 H NMR δ 1.50 (s,} 3H), 2.86 (s, 6H), 3.99 (d, J = 8.4 Hz, 2H), 5.47 (t, J = 8.4 Hz, 1H), 6.90 (s, 1H), 7.53 (t, J = 7.6 Hz, 2H), 7.64 (t, J = 7.6 Hz, 1H), 7.87 (d, J = 8.0 Hz, 2H) ppm; ¹³ C NMR? 11.5, 42.6, 56.5, 114.6, 128.4, 129.1, 133.6, 135.5, 138.8, 143.0 ppm; IR (KBr) 2991, 2926, 1637, 1563, 1455, 1310, 1250, 1175, 1142, 1096, 1063, 923, 895, 778, 741, 689, 540 cm ^-1 ; ^{HRMS (CI +) calcd for C} 13 H 19 N 2 O 2 S 267.1167, found 267.1171.

Production Example 3

Synthesis of Formula 11

[( E ) -1,1-Dimethyl-2 - (( E ) -2-methyl-4- (phenylthio) but-2-enylidene) hydrazine]

To a solution of ( E ) -2-methyl-4- (phenylthio) but-2-enal (3.30 g, 17.16 mmol) and dimethylhydrazine hydrochloride salt (2.48 g, 25.75 mmol) in CH ₂ Cl ₂ ) Was added to the stirred mixture and Et ₃ N (5.20 g, 51.48 mmol) was added. The mixture was stirred at room temperature under argon atmosphere for 1 hour, diluted with CH ₂ Cl ₂ (50 mL) and separated into 4% KOH solution (50 mL). The organic layer was separated, dried over anhydrous K ₂ CO ₃ , filtered and concentrated under reduced pressure to give a crude product. This was purified by SiO ₂ flash column chromatography to obtain yellow oil (Formula 11b, 2.543 g, 10.85 mmol) (yield: 63%).

Data for formula 11: R _f = 0.54 (8: 2 hexane: EtOAc); ¹ H NMR? 1.80 (s, 3H), 2.83 (s, 6H), 3.73 (d, J = 8.0 Hz, 2H), 5.63 -7.22 (m, 1H), 7.24-7.31 (m, 2H), 7.33-7.38 (m, 2H) ppm; ¹³ C NMR? 11.5, 32.3, 42.8, 42.8, 125.9, 126.1, 128.7, 129.8, 136.2, 137.5, 137.9 ppm; IR (KBr) 2970, 2861, 2789, 1699, 1581, 1483, 1448, 1260, 1140, 1089, 1029, 906, 852, 743, 694 cm ^-1 ; ^{HRMS (FAB +) calcd for C} 13 H 19 N 2 S 235.1269, found 235.1262.

Production Example 4

Synthesis of Formula 12b

[( E ) -3 - (( E ) - (2,2-dimethylhydrazono) methyl) -3-methyl-5- (phenylthio) pent-

To a stirred solution of (11) in THF (15 mL) at -78 <0> C was added a 1 M THF solution of NaHMDS (2.89 mL, 2.89 mmol). The mixture was stirred for 30 minutes and acetaldehyde (0.47 g, 10.84 mmol) was added. The resulting mixture was kwinchi (quench) with stirring at -78 ℃ for 3.5 hours, 10% NH ₄ Cl solution (10 mL). Extracted with EtOAc, anhydrous Na ₂ SO ₄ and concentrated under unpurified dried, filtered, and reduced pressure on the product (crude product) was obtained. This was purified by silica gel flash column chromatography to obtain yellow oil (Formula 12b, 0.58 g, 2.08 mmol) (Yield: 70%).

After purification by silica gel flash column chromatography, the compound of Formula 11 (0.29 g, 1.26 mmol) and acetaldehyde (0.28 g, 6.28 mmol) were added thereto using t- BuLi (1.7 M hexane solution, mmol) was obtained (in THF 10 mL, -78 [deg.] C, for 2.5 hours) (yield 48%).

Data for formula 12b: R _f = 0.22 (hexane: EtOAc = 5: 1); ^{1 H NMR δ 1.14 (d,} J = 6.4 Hz, 3H), 1.17 (s, 3H), 2.75 (s, 6H), 4.00 (dq, J d = 2.0, J t = 6.4 Hz, 1H), 4.50 ( 1H), 7.18 (d, J = 15.6 Hz, 1H), 6.21 (d, J = 15.6 Hz, 1H) (m, 4 H) ppm; ¹³ C NMR? 17.3, 21.0, 42.9, 48.6, 72.5, 123.3, 126.3, 128.9, 129.1, 136.0, 138.1, 142.1 ppm; IR (KBr) 3430, 2985, 2872, 2798, 1596, 1488, 1451, 1381, 1255, 1128, 1091, 1021, 955, 922, 829, 740, 689, 628 cm ^-1 ; ^{HRMS (CI +) calcd for C} 15 H 23 N 2 OS 279.1531, found 279.1535.

Production Example 5

Synthesis of Formula 13a

[(4 E , 6 E ) -6- (2,2-Dimethylhydrazono) -5-methyl-3- (phenylsulfonyl) hex-4-en-

To a stirred solution of 1 (0.26 g, 0.97 mmol) in THF (10 mL) at -78 <0> C was added a 1 M THF solution of NaHMDS (1.16 mL, 1.16 mmol). The mixture was stirred for 30 min and acetaldehyde (0.19 g, 4.36 mmol) was added. The resulting mixture was stirred at-78 C for 2.5 h, quenched with 10% NH ₄ Cl solution (10 mL), extracted with EtOAc, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated under reduced pressure to give A crude product was obtained. This was purified by silica gel flash column chromatography to obtain a pale yellow solid (Formula 13a, 0.09 g, 0.29 mmol) (yield: 30%).

(0.17 g, 0.65 mmol) and acetaldehyde (0.14 g, 3.27 mmol) using t- BuLi (1.7 M hexane solution, 0.46 mL, 0.78 mmol) 78 &lt; 0 &gt; C, 2.5 h) and purification by silica gel flash column chromatography afforded 13a (39% yield).

Data for formula 13a: R _f = 0.32 (hexane: EtOAc = 3: 2); mp 120-123 [deg.] C; ^{1 H NMR δ 1.19 (d,} J = 6.4 Hz, 3H), 1.38 (d, J = 1.6 Hz, 3H), 2.86 (s, 6H), 3.13 (d, J = 2.4 Hz, 1H), 3.89 (dd , J = 11.2, 1.6 Hz, 1H), 4.79 (dq, J d = 1.6, J q = 6.4 Hz, 1H), 5.73 (d, J = 11.2 Hz, 1H), 6.97 (br s, 1H), 7.50 -7.56 (m, 2H), 7.62-7.67 (m, 1H), 7.82-7.88 (m, 2H) ppm; ¹³ C NMR? 11.7, 20.6, 42.6, 65.0, 69.6, 115.6, 128.7, 129.0, 133.9, 135.7, 137.9, 144.2 ppm; IR (KBr) 3474, 2978, 2937, 1553, 1442, 1363, 1321, 1289, 1257, 1225, 1141, 1099, 1053, 928, 901, 835, 725, 673 cm ^-1 ; ^{HRMS (CI +) calcd for C} 15 H 23 N 2 O 3 S 311.1429, found 311.1427.

Production Example 6

Synthesis of Formula 15a

[( E ) -1,1-Dimethyl-2 - (( E ) -2-methyl-4- (phenylsulfonyl) pent-2-enylidene) hydrazine]

To a stirred solution of 1 (0.29 g, 1.08 mmol) in THF (10 mL) at -78 <0> C was added a 1 M THF solution of NaHMDS (1.30 mL, 1.30 mmol). The mixture was stirred for 30 min and iodomethane (0.77 g, 5.42 mmol) was added. The resulting mixture was stirred at -78 &lt; 0 &gt; C for 30 minutes and then at room temperature for 2.5 hours. The reaction mixture was quenched with 10% NH ₄ Cl solution (10 mL), extracted with EtOAc, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated under reduced pressure to give a crude product. This was purified by silica gel flash column chromatography to obtain yellow oil (15a, 0.10 g, 0.36 mmol) (yield: 43%).

Using t- BuLi (1.7 M hexane solution, 0.52 mL, 0.88 mmol) as a base, (0.19 g, 0.73 mmol) and iodomethane (0.20 g, 1.46 mmol) (in THF 10 mL, 30 minutes at -78 ° C and 2.5 hours at room temperature) and purification by silica gel flash column chromatography 15a (0.11 g, 0.38 mmol) was obtained (yield: 52%).

Data for formula 15a: R _f = 0.62 (hexane: EtOAc = 3: 2); ^{1 H NMR δ 1.43 (d,} J = 1.2 Hz, 3H), 1.51 (d, J = 6.8 Hz, 3H), 2.85 (s, 6H), 4.08 (dq, J d = 10.4, J q = 6.8 Hz, 1H), 5.29 (d, J = 10.4 Hz, 1H), 6.88 (br s, 1H), 7.48-7.56 (m, 2H), 7.60-7.65 (m, 1H), 7.81-7.88 (m, 2H) ppm ; ¹³ C NMR? 11.7, 14.0, 42.7, 60.1, 122.7, 128.9, 129.0, 133.5, 135.8, 137.7, 141.1 ppm; IR (KBr) 2950, 2873, 2797, 1632, 1571, 1456, 1319, 1157, 1095, 1010, 890, 876, 824, 772, 733, 691, 643 cm ^-1 ; HRMS (CI ⁺ ) calcd for C ₁₄ H ₂₁ N ₂ O ₂ S 281.1324, found 281.1324.

Production Example 7

Synthesis of Formula 15b

[( E ) -1,1-Dimethyl-2 - (( E ) -2-methyl-4- (phenylthio) pent-2-enylidene) hydrazine]

To a stirred solution of compound 11 (0.21 g, 0.90 mmol) in THF (10 mL) at -78 <0> C was added a 1 M THF solution of NaHMDS (1.09 mL, 1.09 mmol). The mixture was stirred for 30 minutes and iodomethane (0.64 g, 4.52 mmol) was added. The reaction mixture was stirred at -78 <0> C for 2.5 h and quenched with 10% NH ₄ Cl solution (10 mL). This was extracted with EtOAc, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated under reduced pressure to give a crude product. This was purified by silica gel flash column chromatography to obtain a yellow oil (15b, 0.040 g, 0.18 mmol) (yield 20%).

The reaction of iodomethane (1.26 g, 8.88 mmol) (in THF 10 mL) with t- BuLi (1.7 M hexane solution, 1.26 mL, 2.14 mmol) At -78 [deg.] C for 30 minutes and then at room temperature for 2.5 hours) and purification by silica gel flash column chromatography afforded 15b (yield 56%).

Data for formula 15b: R _f = 0.67 (hexane: EtOAc = 4: 1); ^{1 H NMR δ 1.38 (d,} J = 6.4 Hz, 3H), 1.65 (s, 3H), 2.82 (s, 6H), 4.19 (dq, J d = 10.0, J q = 6.4 Hz, 1H), 5.44 ( d, J = 10.0 Hz, 1H), 6.95 (br s, 1H), 7.22-7.29 (m, 3H), 7.38-7.43 (m, 2H) ppm; ¹³ C NMR? 11.7, 21.3, 42.2, 42.9, 127.3, 128.7, 133.2, 133.7, 134.7, 135.1, 138.4 ppm; IR (KBr) 3071, 2974, 2865, 2784, 1571, 1480, 1448, 1380, 1275, 1193, 1120, 1034, 915, 847, 752, 705 cm ^-1 ; ^{HRMS (CI +) calcd for C} 14 H 21 N 2 S 249.1425, found 249.1424.

Production Example 8

Synthesis of Formula 3a

[(2 E ,2' E ) -2,2 '- ((2 E ,2' E , 6 E , 6 ' E 8,8'-Sulfonylbis (2,6-dimethyl-4- (phenylsulfonyl) octa-2,6-dien-8-yl-

T- BuOK (0.70 g, 6.37 mmol) was added to a stirred solution of the compound of Formula 1 (1.50 g, 5.31 mmol) in DMF (20 mL) at -20 ° C. The mixture was stirred at -20 &lt; 0 &gt; C for 30 minutes, and a solution of the compound of Formula 2 (0.70 g, 2.66 mmol) (in DMF 2 mL) was added. The resulting mixture was stirred at -20 &lt; 0 &gt; C for 2 hours and at room temperature for 2 hours. It was then quenched with 10% NH ₄ Cl solution (10 mL), extracted with CH ₂ Cl ₂ , washed with 10% NH ₄ Cl, dried over anhydrous Na ₂ SO ₄ , filtered and concentrated under reduced pressure to give A crude product was obtained. This was purified by SiO ₂ flash column chromatography to obtain a pale yellow solid (Formula 3a, 1.40 g, 1.92 mmol) (yield: 72%).

Data for formula 3a: R _f = 0.05 (2: 3 EtOAc / hexane); mp 144-146 [deg.] C; ^{1 H NMR δ 1.33 (d,} J = 1.2 Hz, 6H), 1.62 (s, 6H), 2.48 (dd, J = 13.6, 11.2 Hz, 2H), 2.84 (s, 12H), 3.01 (dd, J = 13.6, 3.2 Hz, 2H), 3.48 (d, J = 7.6 Hz, 2H), 4.09 (ddd, J = 11.2, 10.0, 3.2 Hz, 2H), 5.14 (d, J = 10.0 Hz, 2H), 5.27 ( t, J = 7.6 Hz, 2H), 6.81 (s, 2H), 7.48-7.55 (m, 4H), 7.60-7.66 (m, 2H), 7.78-7.84 (m, 4H) ppm; ¹³ C NMR? 11.7, 16.7, 37.9, 42.7, 51.3, 63.2, 114.2, 129.8, 129.0, 129.1, 129.3, 133.8, 137.5, 140.8, 142.8 ppm; IR (KBr) 2936, 2868, 2791, 1696, 1637, 1565, 1453, 1313, 1155, 1092, 1051, 754, 695, 609 cm ^-1 ; HRMS (FAB ⁺ ) calcd for C ₃₆ H ₅₁ N ₄ O ₆ S ₃ 731.2971, found 731.2975.

Production Example 9

Synthesis of Formula 3b

[(2 E ,2' E ) -2,2 '- ((2 E , 6 E ,8 E , 10 E , 14 E 2,6,11,15-Tetramethyl-4,13-bis (phenylsulfonyl) hexadeca-2,6,8,10,14-pentaene-1,16-diylidene) bis (1,1-dimethylhydrazine)

T- BuOH (5 mL) and C ₂ Cl ₆ (0.36 g, 1.53 mmol) were added to a stirred solution of the compound of Formula 3a (0.56 g, 0.76 mmol) in CH ₂ Cl ₂ (20 mL). The mixture was stirred at room temperature for 10 minutes and KOH (0.43 g, 7.66 mmol) was added. The reaction mixture was stirred at room temperature for 2 hours and most of the solution was removed under reduced pressure. The crude product was diluted with CH ₂ Cl ₂ , washed with 10% NaHCO ₃ , dried over anhydrous K ₂ CO ₃ , filtered and concentrated under reduced pressure. This was purified by SiO ₂ flash column chromatography to obtain a pale yellow solid (Formula 3b, 0.28 g, 0.42 mmol) (yield: 56%).

Data for formula 3b: _Rf = 0.28 (2: 3 EtOAc / hexane); mp 131-134 [deg.] C; ^{1 H NMR δ 1.35 (s,} 6H), 1.66 (s, 6H), 2.44 (dd, J = 12.8, 12.0 Hz, 2H), 2.84 (s, 12H), 3.02 (dd, J = 12.8, 2.8 Hz, 2H), 4.11 (ddd, J = 12.0, 10.4, 2.8 Hz, 2H), 5.24 (d, J = 10.4 Hz, 2H), 5.80-5.92 (br s, 2H), 7.45-7.58 (m, 4H), 7.56-7.66 (m, 2H), 7.67-7.88 (m, 4H) ppm; ¹³ C NMR? 11.6, 16.6, 37.9, 42.6, 63.8, 121.3, 127.8, 128.9, 129.1, 129.3, 133.1, 133.6, 135.7, 137.8, 142.3 ppm; IR (KBr) 2933, 2866, 2791, 1697, 1453, 1311, 1151, 1088, 1039, 919, 746, 697, 613 cm ^-1 ; HRMS (FAB ⁺ ) calcd for C ₃₆ H ₄₉ N ₄ O ₄ S ₂ 665.3195, found 665.3208.

Production Example 10

Synthesis of Compound 3c [Crocetin dimethylhydrazone]

KOMe (1.40 g, 19.87 mmol) was added to a stirred solution of compound 3b (0.44 g, 0.66 mmol) in benzene (12 mL) and cyclohexane (18 mL). The reaction mixture was heated at 80 &lt; 0 &gt; C for 8 hours and cooled to room temperature. It was then filtered through celite and concentrated under reduced pressure to give a crude product. This was diluted with CH ₂ Cl ₂ , washed with 10% NaHCO ₃ solution, dried over anhydrous K ₂ CO ₃ , filtered and concentrated under reduced pressure to give a crude solid (crude conjugated polyene hydrazone 3c, 0.22 g, 0.58 mmol) Yield: 88%). MeOH to prepare analytical samples.

Data for formula 3c: _Rf = 0.50 (1: 4 EtOAc / hexane); mp 115-118 [deg.] C; ^{1 H NMR δ 1.98 (s,} 6H), 2.02 (s, 6H), 2.90 (s, 12H), 6.20-6.32 (m, 2H), 6.23 (d, J = 11.6 Hz, 2H), 6.35 (d, J = 14.8 Hz, 2H), 6.58-6.69 (m, 2H), 6.68 (dd, J = 14.8, 11.6 Hz, 2H), 7.03 (s, 2H) ppm; ¹³ C NMR? 12.1, 12.8, 43.0, 124.9, 130.0, 131.1, 132.6, 135.8, 136.5, 137.1, 138.5 ppm; UV (CH ₂ Cl ₂ )? Max (?) 443 (167,508), 472 (226, 396), 495 (197,984) nm; IR (KBr) 2996, 2923, 2788, 1544, 1476, 1404, 1273, 1051, 965, 906, 802 cm &lt; ^{-1 &} gt ;; HRMS (FAB ⁺ ) calcd for C ₂₄ H ₃₆ N ₄ 380.2940, found 380.2946.

Production Example 11

Synthesis of Compound 3 [Crocetin dinitrile]

Urea-hydrogen peroxide (0.33 g, 3.47 mmol) and phthalic anhydride (0.26 g, 1.73 mmol) were mixed in acetonitrile (10 mL) and stirred at room temperature for 2 hours A clear solution was obtained. The crude product, in CH ₂ Cl ₂ , was added 3c and the reaction mixture was stirred at room temperature for 2 hours. Most of the solvent was removed under reduced pressure. This was removed by filtration undiluted solid was dissolved in CHCl _3. The filtrate was concentrated under reduced pressure and the crude product was recrystallized from MeOH to obtain a red solid (Formula 3, 0.10 g, 0.35 mmol) (yield: 60%).

Data of formula 3: R _f = 0.47 (1: 4 EtOAc / hexane); mp 100-103 [deg.] C; ^{1 H NMR δ 1.97 (s,} 6H), 2.01 (s, 6H), 6.35-6.44 (m, 2H), 6.45 (dd, J = 14.8, 10.8 Hz, 2H), 6.55 (d, J = 14.8 Hz, 2H), 6.67-6.77 (m, 2H), 6.81 (d, J = 10.8 Hz, 2H) ppm; ¹³ C NMR? 12.7, 15.3, 106.4, 121.7, 122.0, 131.7, 136.5, 143.9, 144.1 ppm; UV (CH ₂ Cl ₂ )? Max (?) 408 (82,824), 430 (128,500), 457 (128,102) nm; IR (KBr) 2992, 2214, 1730, 1686, 1619, 1587, 1453, 1390, 1153, 1063, 974, 916, 732, 656 cm ^-1 ; ^{HRMS (FAB +) calcd for C} 20 H 22 N 2 290.1783, found 290.1780.

Claims (21)

A C5 sulfone compound represented by the following formula (1).
[Chemical Formula 1]

A process for producing a C5 sulfone compound represented by the following formula (1), which comprises mixing a compound represented by the following formula (1a), a hydrazine and an amine compound.
[Chemical Formula 1]

[Formula 1a]

The method of claim 2,
Wherein the compound represented by Formula 1a is dissolved in an organic solvent to prepare a solution.
The method of claim 3,
Wherein the organic solvent is CH ₂ Cl ₂ .
The method of claim 2,
Wherein the hydrazine is 1,1-dimethylhydrazine.
The method of claim 2,
Wherein the amine compound is triethylamine.
The method of claim 2,
Further comprising the step of purifying the compound by column chromatography after the mixing step.
A crocetin dinitrile represented by the following formula (3).
(3)

The method of claim 8,
The crocetin dinitrile represented by the formula (3) is prepared by using a sulfonic compound represented by the following formula (1).
[Chemical Formula 1]

A process for producing crocetin dinitrile represented by the following formula (3), comprising reacting a C5 sulfone compound represented by the following formula (1) with a compound represented by the following formula (2).

[Chemical Formula 1]

(2)

(3)

The method of claim 10,
Wherein the step of reacting is carried out by adding a basic substance in an organic solvent and reacting.
The method of claim 11,
Lt; RTI ID = 0.0 &gt; t- BuOK. &Lt; / RTI &gt;
The method of claim 10,
And a step of producing a compound represented by the following formula (3a) by the above reaction.
[Chemical Formula 3]

14. The method of claim 13,
(B) a step of reacting the organic solvent with a basic substance, a chlorine-providing substance, and a compound represented by the general formula (3a), and then reacting the compound represented by the general formula Process for preparing crocetin dinitrile.
(3b)

15. The method of claim 14,
Wherein the basic substance comprises at least one selected from the group consisting of t- BuOH and KOH.
15. The method of claim 14,
(C) adding a basic substance to the organic solvent and a compound represented by the formula (3b), and reacting the organic solvent with the compound represented by the formula (3b) to produce a compound represented by the following formula (3c).
[Chemical Formula 3c]

18. The method of claim 16,
Wherein the basic substance is KOMe.
18. The method of claim 16,
The method according to claim 1, further comprising the step d) of reacting the compound represented by Formula 3c with an acetonitrile solution mixed with urea-hydrogen peroxide and phthalic anhydride after the step c).
The method according to claim 11, claim 14 or claim 16,
The organic solvent may be DMF, CH ₂ Cl ₂ , C ₂ Cl ₆ , CHCl ₃ , Benzene, and cyclohexane. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt;
An organic molecular lead comprising a crocetin dinitrile according to claim 8 or 9.
10. A compound for an electronic device comprising the crocetin dinitrile according to claim 8 or 9.