WO2019147015A1

WO2019147015A1 - Efficient synthesis method of c20 polyene bis(phosphonate) and carotene compound using same

Info

Publication number: WO2019147015A1
Application number: PCT/KR2019/000964
Authority: WO
Inventors: 구상호; 김다혜; 김윤지
Original assignee: 명지대학교 산학협력단
Priority date: 2018-01-26
Filing date: 2019-01-23
Publication date: 2019-08-01
Also published as: KR20190091139A; KR102092655B1

Abstract

The present invention relates to an intermediate necessary for producing a carotene compound having excellent antioxidant activity with various aldehyde compounds in a single step reaction, a synthesis method thereof, and a synthesis method of various carotene compounds using the same. For this purpose, a novel tetraethyl (2,6,11,15-tetramethylhexadeca-2,4,6,8,10,12,14-heptaen-1,16-diyl)bis(phosphonate) represented by structural formula 2 and diethyl (4-(benzo[d]thiazole-2-ylsulfonyl)-2-methyl-2-buten-1-yl) phosphonate of structural formula 5, and an efficient synthesis method thereof are proposed. When using C₂₀ polyene bis(phosphonate) of structural formula 2, the carotene compound of various structures can be produced by a single step reaction with various aldehyde compounds, so that the reaction is efficient and simple.

Description

Efficient synthesis of C20 polyenes (phosphonates) and carotene compounds using them

The present invention is an antioxidant or a functional food as food coloring, medicines, and carotene compounds of novel represented by the following structural formula 1, which can be used as cosmetic ingredients, for efficiently synthesized in this appropriate formula 2 novel C ₂₀ polyenes service represented by (Phosphonate) compound, a method for synthesizing the same, and a method for easily synthesizing the carotene compound by reacting it with various aldehyde compounds.

[Structural formula 1]

Wherein R may be selected from the group consisting of alkyl, aryl, aralkyl, and heteroaryl having 5 to 20 carbon atoms.

[Structural formula 2]

Natural carotene compounds such as lycopene, zeaxanthin, canthaxanthin, and astaxanthin, as well as beta-carotene, commonly contain the polyene chain structure represented by Structural Formula (1). They are known to have an antioxidative effect by reacting with active oxygen in living organisms and efficiently removing it, and it plays an important role in photosynthesis in absorbing light and transferring energy together with chlorophyll. Since carotene compounds have various industrial uses such as livestock feeds, food additives, health supplements, medicines, and cosmetic raw materials, studies on efficient synthesis of these carotene compounds are continuing.

As a general method for synthesizing a carotene compound, an alpha, beta-unsaturated ketone compound [structural formula B] is synthesized by reacting an aldehyde compound [structural formula A] with acetone as shown in the following figure, (HX) and triphenylphosphine (PPh ₃ ) are sequentially reacted to synthesize the compound [structural formula C], and then the biotite salt represented by the structural formula 3 is produced. Finally, two equivalents of biotite salt [structural formula 3] and one equivalent of 2,7-dimethyl-2,4,6-octatriendial represented by structural formula 4 were reacted to prepare a carotene compound containing a conjugated polyene chain [ (Angew. Chem. 1960, 72, 911-915; Angew. Chem. 1977, 89, 437-443).

The above method utilizes a C ₁₀ dialdehyde compound of the structural formula 4 that is efficiently used in the synthesis of a carotene compound. In order to combine the C ₁₀ dialdehyde compound with the aldehyde compound [structural formula A] . That is, in order to prepare the various carotene compounds represented by the structural formula 1, it is necessary to prepare various biotite salts represented by the structural formula 3 through various steps of reaction from the respective aldehyde compounds [structural formula A].

Wherein R may be selected from the group consisting of alkyl, aryl, aralkyl and heteroaryl having between 5 and 20 carbon atoms.

In the conventional method as described above, there is a problem that a long reaction step is required to form a biotite salt from each aldehyde compound through a chain extension reaction. Thus, a carotene compound having various structures can be easily and rapidly prepared from each aldehyde compound There is a need for a new way to do this.

Therefore, in order to more efficiently prepare the various carotene compounds represented by the structural formula 1, it is possible to carry out various reaction steps from the aldehyde compound [structural formula A] to produce the various biotite salts of the structural formula 3, It is intended to provide a compound such as the structural formula 2 in which the polyene chain is extended and contains a phosphine group, which can directly react with various aldehydes [structural formula A] as described above to directly provide a carotene compound.

When the polyene compound of formula 2 is reacted with various aldehyde compounds [formula A], the various carotene compounds of formula 1 can be prepared in a single step reaction, so that the reaction proceeds efficiently and economically, And can be manufactured easily and quickly.

In the present invention, a carotene compound having various structures represented by the structural formula 1 is prepared by using 2,7-dimethyl-2,4,6-octatrienediar represented by the structural formula 4 according to the conventional method using the Biathyer reaction To solve the problem of making various biotite salts of the structural formula 3 containing a phosphine group by extending the chain through an aldehyde compound [structural formula A] in several steps. For this purpose, a novel polyene compound, which is required for the production of a carotene compound having various structures represented by the structural formula 1 by a single step reaction with various aldehyde compounds [structural formula A], a method for producing the same, We propose a simple and efficient method for synthesizing the compounds.

In order to solve the above problems, the present invention provides a novel C ₂₀ polyenbis represented by the structural formula 2 required for the simple and efficient synthesis of various carotene compounds from various aldehyde compounds (structural formula A) Nate) compound, a method for producing the same, and various carotene compounds represented by the structural formula 1 using the same, and a method for efficiently synthesizing the same.

The first technical object of the present invention is to provide a novel tetraethyl (2,6,11,15-tetramethylhexadeca-2,4,6,8,10,12,14-heptaene -1, 16-diyl) bis (phosphonate).

[Structural formula 2]

A second technical objective of the present invention is to provide a process for the preparation of tetraethyl (2,6,11,15-tetramethylhexadeca-2,4,6,8,10,12,14-heptaen-1,16 (Benzo [ d ] thiazol-2-ylsulfonyl) -2-methyl-2-buten-l-yl) -bis (phosphonate) To provide a phosphonate.

[Structural Formula 5]

A third technical object of the present invention is to provide a novel diethyl (4- (benzo [ d ] thiazole-2-ylsulfonyl) -2-methyl- And to provide a method for producing a phenate.

The method comprises: (a) preparing a chlorohydrin compound represented by formula D from isoprene;

(b) a step of brominating an allylic alcohol represented by the structural formula D to produce an allyl halide compound represented by the structural formula E;

(c) reacting the allyl halide compound represented by the structural formula E with 2-mercaptobenzothiazole to prepare a chloroallylic sulfide compound represented by the structural formula F;

(d) preparing a chloroallylic sulfone compound represented by Structural Formula G by oxidation reaction of chloroallylic sulfide compound represented by Structural Formula F; And

(e) A novel compound represented by Structural Formula 5 containing a diethylphosphonate group by Arbuzov reaction between allylic chloride of the compound represented by Structural Formula G and triethylphosphite [P (OEt) ₃ ] (Benzo [ d ] thiazole-2-ylsulfonyl) -2-methyl-2-buten-1-yl) phosphonate.

The chlorohydrin formation reaction of isoprene in the step (a) can be carried out using N-chlorosuccinimide (NCS) in an aqueous solution, and it is preferable to mix a polar organic solvent such as DMF at a volume ratio of about 10%.

In the step (b), the bromination reaction of the allylic alcohol proceeds at 0 ° C to room temperature using PBr ₃ , and copper (Cu-X) is preferably added as a catalyst for the allylic rearrangement reaction.

In the step (c), the nucleophilic substitution reaction of the allylic bromide and the 2-mercaptobenzothiazole of the compound represented by the structural formula E is preferable in terms of the position-selective reaction of K ₂ CO ₃ as a base in an acetone solvent.

In step (c), the allylic halide compound represented by the structural formula E and the 2-mercaptobenzothiazole may be reacted in an equivalent ratio of 1: 1. Wherein the 2-mercaptobenzothiazole can react with an allylic bromide group.

The oxidation of the sulfide group to sulfone in step (d) can be carried out using H ₂ O ₂ and various metal catalysts or by using an organic oxidizing agent such as peracetic acid, MCPBA (meta-chloroperbenzoic acid) or mono perphthalic acid have.

In the step (e), the Arbuzov reaction is preferably carried out by activating allylic chloride with allylic iodide in a Finkelstein reaction (NaI, acetone) and reacting with triethylphosphite.

A fourth technical object of the present invention is to provide a process for producing a diethyl (4- (benzo [ d ] thiazole-2-ylsulfonyl) -2-methyl- (2,6,11,15-tetramethylhexadeca-2,4-dione represented by the structural formula 2) by reacting 2,7-dimethyl-2,4,6- 6,8,10,12,14-heptaen-1,16-diyl) bis (phosphonate).

In the above reaction, the compound represented by Formula 5 and the compound represented by Formula 4 can be reacted at an equivalent ratio of 2: 1.

The reaction is preferably carried out at a low temperature of -78 ° C to 0 ° C using a base such as NaHMDS or KHMDS in an aprotic solvent such as THF or DME.

A fifth technical objective of the present invention is to provide a process for preparing various carotene compounds of formula 1 by reacting a C ₂₀ polyenes (phosphonate) compound of formula 2 with various aldehyde compounds [formula A].

The above-mentioned alkyl, aryl or aralkyl, and heteroaryl may have a substituent.

More specifically, in the above formula, R is

,

,

,

,

,

And

&Lt; / RTI >

In the above reaction, the compound represented by the structural formula A and the compound represented by the structural formula 2 can be reacted at an equivalent ratio of 2: 1.

The above process is preferably carried out by heating the mixture at a temperature of 100 ° C or higher using a metal alkoxide base in a mixed solvent of alcohol and toluene.

A sixth and final technical objective of the present invention is to provide a process for the preparation of a compound of formula (I), which is efficiently produced by a single step reaction of a C ₂₀ polyenes (phosphonate) compound of formula 2 with various aldehyde compounds [formula A] 1 to < RTI ID = 0.0 > 1-9. &Lt; / RTI >

[Structural formula 1-1]

[Structural formula 1-2]

[Structural Formula 1-3]

[Structural Formula 1-4]

[Structural Formula 1-5]

[Structural formula 1-6]

[Structural formula 1-7]

[Structural formula 1-8]

[Structural formula 1-9]

Tetraethyl (2,6,11,15-tetramethylhexadeca-2,4,6,8,10,12,14-heptaen-1,16-diyl) bis (Phosphonates) efficiently and easily provide various types of carotene compounds represented by the structural formula 1 in a single step reaction with various aldehyde compounds [structural formula A].

The diethyl (4- (benzo [ d ] thiazol-2-ylsulfonyl) -2-methyl-2-buten-1-yl) phosphonate of the newly prepared formula 5 has the structure 2, (2,6,11,15-tetramethylhexadec-2-ene) represented by the above structural formula 2 which can be used in the synthesis of a carotene compound by a single step reaction with 7-dimethyl- , 4,6,8,10,12,14-heptaen-1,16-diyl) bis (phosphonate) efficiently and easily.

The novel carotene compounds of the structural formulas 1-1 to 1-9 prepared according to the present invention exhibit antioxidative ability by reacting with active oxygen and radicals and can be used for a variety of purposes including livestock feeds, food additives, health supplements, medicines, It is a substance that is used for industrial purposes.

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.

Example 1. A compound represented by [Structural formula D]

1-Chloro-2-methylbut-3-en-2-ol.

(24.0 mL, 0.24 mol) and N -chlorosuccinimide (NCS, 26.7 g, 0.20 mol) were added to a mixed solution of distilled water (100 mL) and DMF (25 mL) Lt; / RTI > for 20 hours. The reaction product was cooled to room temperature, extracted with diethyl ether, dried over anhydrous Na ₂ SO ₄ , filtered through filter paper, and the filtrate was concentrated under reduced pressure to obtain a colorless liquid chlorohydrin [formula D] (18.8 g, 0.16 mol) Was obtained in a yield of 78%. Data for [structural formula D]: [R _f = 0.44 (4: 1 hexane: EtOAc)]; ^{1 H NMR δ = 1.38 (s} , 3H), 2.17 (br s, 1H), 3.53 (A of ABq, J AB = 10.8 Hz, 1H), 3.57 (B of ABq, J AB = 10.8 Hz, 1H), (Dd, J = 10.7, 1.0 Hz, 1H), 5.38 (dd, J = 17.3, 1.0 Hz, 1H), 5.92 (dd, J = 17.3, 10.7 Hz, 1H) ppm; ¹³ C NMR? = 25.3, 54.0, 72.5, 114.7, 141.9 ppm.

Example 2. A compound represented by the structural formula E

4-Bromo-1-chloro-2-methylbut-2-ene.

(13.8 g, 0.12 mol) was dissolved in benzene (80 mL) and THF (10 mL) under argon atmosphere and then CuI (220 mg, 1.15 mmol) and PBr ₃ , 46.03 mmol) were added sequentially. The reaction mixture was stirred at 0 ° C for 2.5 hours, then filtered through a pad of silica gel and washed with a 3: 1 by volume mixed solvent of diethyl ether / hexane. The filtrate was concentrated under reduced pressure to obtain a yellow liquid of 4-chloroallylic bromide [structural formula E] (19.50 g, 0.11 mol, E / Z = 5: 1) in a yield of 92%. Data for [formula E]: _Rf = 0.73 (4: 1 hexane: EtOAc); ^{1 H NMR δ = 1.85 (s} , 3H), 3.98 (dd, J = 8.3, 0.9 Hz, 2H), 4.03 (s, 2H), 5.87 (dt, J t = 8.3, J d = 0.9 Hz, 1H) ppm; ¹³ C NMR? = 14.1, 27.3, 50.6, 125.3, 137.8 ppm.

Example 3. Synthesis of Compound Represented by Structural Formula F

2 - ((4-Chloro-3-methylbut-2-en-1-yl) thio) benzo [d] thiazole.

(19.49 g, 0.106 mol) was dissolved in acetone (100 mL) under an argon atmosphere and then 2-mercaptobenzothiazole (16.15 g, 96.57 mmol) and anhydrous K ₂ CO ₃ (20.02 g, 0.145 mol) was added sequentially. The reaction mixture was stirred at a temperature of 0 ° C for 2 hours, then allowed to warm to room temperature and stirred well for 11 hours. Dilute the reaction product with diethyl ether, wash with water, 10% sodium hydrogencarbonate solution and brine solution. The aqueous solution was extracted again with diethyl ether, and the combined organic layers were dried over anhydrous Na ₂ SO ₄ , filtered through filter paper and the filtrate was concentrated under reduced pressure to obtain a chloroallylic sulfide compound [structural formula F] (27.05 g, 0.100 mol, E : Z = 7: 1) was obtained in a yield of 95%. Data for [formula F]: _Rf = 0.61 (1: 4 EtOAc / hexane); ^{1 HNMR δ = 1.90 (s,} 3H), 4.02 (s, 2H), 4.03 (d, J = 7.6 Hz, 2H), 5.82 (t, J = 7.6 Hz, 1H), 7.30 (t, J = 8.0 Hz 8.0 Hz, 1H), 7.42 (t, J = 8.0 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.87 (d, J = 8.0 Hz, 1H) ppm; ¹³ CNMR? = 14.4, 30.9, 51.0, 120.8, 121.4, 123.7, 124.1, 125.9, 135.2, 136.7, 153.0, 165.8 ppm; IR (KBr) 2989, 1473, 1436, 1321, 1275, 1243, 1078, 1004, 871, 765, 687, 724 cm < ^{-1 &} gt ;; HRMS (CI) calcd for C ₁₂ H ₁₃ ClN ₂ 270.0178, found 270.0180.

Example 4. A compound represented by the structural formula G

2 - ((4-Chloro-3-methylbut-2-en-1-yl) sulfonyl) benzo [d] thiazole.

Acetonitrile (150 mL) is added to Urea-H ₂ O ₂ (44.35 g, 0.47 mmol) and anhydrous phthalic acid (38.90 g, 0.236 mol) under an argon atmosphere. The mixture was stirred at room temperature for 1.5 hours to obtain a colorless mono-phthalic acid solution. 4-Chloroallyl sulfide [formula F] (21.20 g, 78.57 mmol) is dissolved in CH ₂ Cl ₂ (10 mL) and the mixture is stirred at room temperature for 12 hours. As a result, the white solid was diluted with CH ₂ Cl ₂ and filtered with a filter paper. The filtrate was washed with water, dried over anhydrous Na ₂ SO ₄ , filtered through filter paper, and the filtrate was concentrated under reduced pressure to obtain an ivory solid. This was purified by recrystallization using methanol to obtain 4-chloroallyl sulfone [formula G] (17.15 g, 56.82 mmol) as a white solid in 72% yield. Data for [structural formula G]: _Rf = 0.22 (1: 4 EtOAc / hexane); ^{1 HNMR δ = 1.70 (s,} 3H), 3.95 (s, 2H), 4.29 (d, J = 7.6 Hz, 2H), 5.66 (t, J = 7.6 Hz, 1H), 7.61 (t, J = 8.0 Hz 8.0 Hz, 1H), 7.66 (t, J = 8.0 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 8.23 (d, J = 8.0 Hz, 1H) ppm; ¹³ CNMR? = 14.0, 49.1, 53.4, 113.1, 121.4, 124.5, 126.8, 127.2, 136.1, 142.3, 151.7, 165.8 ppm; IR (KBr) 2986, 2924, 1558, 1473, 1398, 1328, 1257, 1140, 1088, 1037, 910, 868, 765, 736, 689 cm ^-1 ; HRMS (CI) calcd for C ₁₂ H ₁₃ ClNO ₂ S ₂ 302.0076, found 302.0075.

Example 5. A compound represented by the structural formula 5

Diethyl (4- (benzo [d] thiazol-2-ylsulfonyl) -2-methylbut-2-en-1-yl) phosphonate.

4-Chloroallyl sulfone [formula G] (12.81 g, 42.44 mmol) is dissolved in acetone (120 mL) and NaI (9.54 g, 63.66 mmol) is added. Higo dilute the reaction mixture to a room temperature in an argon atmosphere under good stirring for 8 hours, and then diethyl ether, washed with water and then dried over anhydrous Na ₂ SO _4, and filtered and concentrated under reduced pressure, there was obtained a yellow solid. This was dissolved in toluene (100 mL), triethyl phosphite (10.9 mL, 63.66 mmol) was added, and the mixture was refluxed for 12 hours to the boiling point of the solvent under an argon atmosphere. After cooling to room temperature, most of the solvent was removed under reduced pressure, and the remaining liquid was purified by silica gel column chromatography (30% -100% acetone / hexane) to give diethylphosphonate , 32.1 mmol, E / Z = 4: 1) was obtained in a yield of 76%. Data for [formula 5]: _Rf = 0.25 (100% EtOAc); 0.32 (50% acetone / hexane); ^{1 H NMR δ = 1.26 (t} , J = 7.2 Hz, 6H), 1.78 (d, J = 2.8 Hz, 3H), 2.59 (d, J = 22.4 Hz, 2H), 4.04 (dq, J d = 7.6, _{J q = 7.2 Hz, 4H)} , 4.30 (dd, J = 7.6, 3.6 Hz, 2H), 5.45 (dt, J d = 5.6, J t = 7.6 Hz, 1H), 7.60 (t, J = 7.6 Hz, 1H), 7.65 (t, J = 7.6 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 8.23 (d, J = 8.0 Hz, 1H) ppm; ^{13 CNMR δ = 16.3 (d,} J = 6.0 Hz), 18.0 (d, J = 2.2 Hz), 37.1 (d, J = 136.9 Hz), 54.5 (d, J = 3.0 Hz), 61.9 (d, J = 6.7 Hz), 113.3 (d, J = 12.6 Hz), 122.3, 125.3, 127.6, 128.0, 136.9, 139.0 (d, J = 11.1 Hz), 152.6, 165.6 ppm; IR (KBr) 3001, 2920, 1741, 1471, 1395, 1338, 1249, 1154, 1017, 969, 855, 770, 732, 690, 637 cm ^-1 ; HRMS (CI) calcd for C ₁₆ H ₂₃ NO ₅ PS ₂ 404.0755, found 404.0759.

Example 6. A compound represented by the structural formula 2

Tetraethyl (2,6,11,15-tetramethylhexadeca-2,4,6,8,10,12,14-heptaene-1,16-diyl) bis (phosphonate)

(1.46 g, 3.62 mmol, 2.9 eq.) Of structure 5 and 2,7-dimethyl-2,4,6-octatrienedi (198 mg, 1.21 mmol, 1 eq.) Is dissolved in THF (36 mL) and cooled to -78 < 0 > C. To this is added slowly 1M NaHMDS (4.0 mL, 4.0 mmol, 3.1 equiv) for 15 min. The pale yellow solution gradually turns red as NaHMDS is added. The mixture is stirred at -78 < 0 > C for 1.5 h, stirred at 0 < 0 > C for 3.5 h and then quenched with 10% ammonium chloride solution. The reaction mixture is extracted with ethyl acetate, washed with brine, dried over anhydrous potassium carbonate, filtered and the filtrate is concentrated under reduced pressure to give 1.52 g of a red liquid. This was purified by silica gel column chromatography (30% -100% acetone / hexane) to obtain tetraethyl bis (phosphonate) (422 mg, 0.78 mmol, all- E / Z = 6 : 1) was obtained in a yield of 64%. Data for [formula 2]: R _f = 0.19 (50% acetone / hexane); ^{1 H NMR δ = 1.31 (t} , J = 7.2 Hz, 12H), 1.94 (s, 6H), 1.96 (d, J = 4.4 Hz, 6H), 2.65 (d, J = 23.2 Hz, 2H), 4.10 ( _{dq, J d = 7.2, J} q = 7.2 Hz, 8H), 6.05 (dd, J = 10.8, 5.6 Hz, 2H), 6.16-6.28 (m, 2H), 6.27 (dd, J = 15.2, 2.4 Hz, 2H), 6.46 (dd, J = 15.2, 10.8 Hz, 2H), 6.56-6.66 (m, 2H) ppm; ^{13 C NMR δ = 12.7, 16.5} (d, J = 6.0 Hz), 18.2 (d, J = 3.0 Hz), 37.5 (d, J = 136.0 Hz), 61.9 (d, J = 6.7 Hz), 127.2 (d J = 6.7 Hz), 128.5 (d, J = 14.2 Hz), 129.8, 130.2 (d, J = 14.1 Hz), 132.2, 136.0, 137.7 (d, J = 6.7 Hz) ppm; IR (KBr) 2995, 2915, 1734, 1679, 1456, 1385, 1251, 1166, 1023, 960, 847, 783, 733 cm ^-1 ; _{HRMS (FAB) calcd for C 28} H 46 O 6 P 2 540.2770, found 540.2769.

Example 7. Synthesis of Compound [1-1]

4,4 '- (3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis (methylbenzene).

Tetraethyl bis (phosphonate) (83 mg, 0.15 mmol) and p -tolualdehyde (92 mg, 0.77 mmol) of the structural formula 2 were dissolved in methanol (30 mL) and toluene (30 mL) 3.84 mmol). The mixture is refluxed for 12 hours at a temperature of 110 < 0 > C under an argon atmosphere and then allowed to cool to room temperature. Most of the solvent is removed under reduced pressure, diluted with diethyl ether and washed with 10% ammonium chloride solution. The aqueous solution is extracted again with CH ₂ Cl ₂ , and the combined organic layers are dried over anhydrous potassium carbonate, filtered, and the filtrate is concentrated under reduced pressure to give a dark red solid. This was purified by recrystallization using methanol to obtain a carotene compound (42 mg, 0.090 mmol, 9- ( Z )) represented by the structural formula 1-1 in red solid at a yield of 58%. Data for 9- (Z) - [Structural Formula ^{1-1]: 1 H NMR δ =} 1.99 (s, 3H), 2.02 (s, 3H), 2.04 (s, 6H), 2.34 (s, 3H), 2.35 ( s, 3H), 6.15 (d , J = 11.6 Hz, 1H), 6.24-6.34 (m, 2H), 6.32 (d, J = 11.6 Hz, 1H), 6.34 (d, J = 14.8 Hz, 1H), 6.41 (d, J = 14.8 Hz , 1H), 6.56 (d, J = 15.6 Hz, 1H), 6.60 (d, J = 15.6 Hz, 1H), 6.59-6.72 (m, 2H), 6.67 (dd, J = 14.8, 11.6 Hz, 1H) , 6.86 (d, J = 16.0 Hz, 1H), 6.88 (dd, J = 14.8, 11.6 Hz, 1H), 7.08-7.20 (m, 4H), 7.30-7.40 (m, 4H), 7.39 (d, J = 16.0 Hz, 1H) ppm; ¹³ C NMR? = 12.8, 12.9, 12.9, 20.9, 21.2, 21.3, 123.6, 124.6, 125.0, 126.2, 126.4, 127.4, 129.1, 129.4, 129.4, 130.1, 130.2, 131.1, 132.7, 132.7, 132.9, 134.0, , 135.0, 135.6, 136.4, 136.5, 136.5, 137.0, 137.3, 137.4, 138.0 ppm; UV (CH ₂ Cl ₂ , c = 1.69 × 10 ^-4 )? (?) = 455 (4,740), 481 (5,640), 514 (4,560) nm; IR (KBr) 3023, 2922, 2855, 1733, 1677, 1606, 1513, 1446, 1375, 1241, 1215, 1182, 1111, 1044, 965, 839, 805, 757 cm ^-1 ; HRMS (FAB) calcd for C ₃₆ H ₄₀ 472.3130, found 472.3133.

Example 8. A compound represented by the formula [1-2]

4,4 '- (3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis (bromobenzene).

(221 mg, 0.41 mmol) and p -bromobenzaldehyde (378 mg, 2.04 mmol) of the structural formula 2 were dissolved in methanol (30 mL) and toluene (30 mL, ) Followed by KOMe (717 mg, 10.22 mmol). The mixture was reacted at 110 ° C. for 12 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain 131 mg (0.217 mmol) of 9- ( Z )) Was obtained in a yield of 53%. Data for 9- (Z) - [Structural Formula ^{1-2]: 1 H NMR δ =} 1.99 (s, 3H), 2.03 (s, 3H), 2.04 (s, 3H), 2.06 (s, 3H), 6.20 ( d, J = 11.2 Hz, 1H ), 6.26-6.34 (m, 2H), 6.35 (d, J = 11.2 Hz, 1H), 6.36 (d, J = 14.8 Hz, 1H), 6.43 (d, J = 14.8 Hz, 1H), 6.50 (d , J = 15.6 Hz, 1H), 6.53 (d, J = 15.6 Hz, 1H), 6.62-6.71 (m, 2H), 6.67 (dd, J = 14.8, 11.2 Hz, 1H ), 6.86 (dd, J = 14.8, 11.2 Hz, 1H), 6.87 (d, J = 15.6 Hz, 1H), 7.29 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.8 Hz, 2H ), 7.41 (d, J = 15.6 Hz, 1H), 7.43 (d, J = 8.8 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H) ppm; ¹³ C NMR? = 12.8, 12.8, 12.9, 20.8, 120.7, 121.1, 123.4, 124.9, 126.0, 126.1, 127.7, 127.7, 128.0, 128.0, 130.3, 130.4, 131.7, 131.7, 131.7, 131.7, 132.1, 133.1, 133.3 , 133.7, 134.2, 136.5, 136.6, 136.7, 137.9, 138.6 ppm; UV (CH ₂ Cl ₂ , c = 8.96 × 10 ^-6 )? (?) = 452 (79,600), 478 (104,800), 510 (86,000) nm; IR (KBr) 3027, 2922, 2855, 1729, 1707, 1588, 1483, 1401, 1245, 1215, 1178, 1103, 1073, 1006, 962, 820, 753, 663, 514 cm ^-1 ; HRMS (FAB) calcd for C ₃₄ H ₃₄ Br ₂ 602.1027, found 600.1032.

Example 9. A compound represented by the formula [1-3]

5,5 '- (3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis (1,3-dimethylbenzene) .

Tetraethyl bis (phosphonate) (176 mg, 0.33 mmol) and 3,5-dimethylbenzaldehyde (218 mg, 1.63 mmol) in the same manner as in Example 7 were dissolved in methanol (30 mL) and toluene (30 mL) mL) and KOMe (570 mg, 8.13 mmol) is added. The mixture was reacted at 110 ° C. for 12 hours under an argon atmosphere and then purified by recrystallization using methanol to obtain a carotene compound represented by the structural formula 1-3 of red solid (81 mg, 0.162 mmol, all- ( E )) Was obtained in a yield of 50%. Data for all- (E) - [Structural Formula ^{1-3]: 1 H NMR δ =} 1.99 (s, 6H), 2.03 (s, 6H), 2.31 (s, 12H), 6.26-6.32 (m, 2H), 6.33 (d, J = 12.4 Hz , 2H), 6.41 (d, J = 14.8 Hz, 2H), 6.53 (d, J = 16.0 Hz, 2H), 6.62-6.69 (m, 2H), 6.68 (dd, J = 14.8, 12.4 Hz, 2H), 6.86 (s, 2H), 6.88 (d, J = 16.0 Hz, 2H), 7.06 (s, 4H) ppm; ¹³ C NMR? = 12.8, 12.9, 21.3, 124.3, 124.3, 125.1, 127.7, 129.0, 130.3, 132.9, 133.0, 133.3, 135.7, 136.6, 137.7, 138.0 ppm; UV (CH ₂ Cl ₂ , c = 1.08 × 10 ^-5 ) λ (ε) = 455 (65,400), 481 (86,500), 515 (72,100) nm; IR (KBr) 3027, 2922, 2855, 1737, 1595, 1558, 1461, 1439, 1394, 1372, 1245, 1029, 1006, 962, 895, 849, 775, 686 cm ^-1 ; HRMS (FAB) calcd for C ₃₈ H ₄₄ 500.3443, found 500.3434.

Example 10. A compound represented by the structural formula 1-4

6,6 '- (3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis 4-tetramethoxy-5-methylbenzene).

Tetraethylbis (phosphonate) (423 mg, 0.78 mmol) and 1,2,3,4-tetramethoxy-5-methylbenzaldehyde (940 mg, 3.91 mmol) in a similar manner to Example 7, Is dissolved in methanol (30 mL) and toluene (30 mL), followed by KOMe (1.37 g, 19.55 mmol). The mixture was reacted at 110 ° C for 24 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain 134 mg of a carotene compound represented by Structural Formula 1-4 (134 mg, 0.187 mmol, all- ( E )) Was obtained in a yield of 24%. Data for all- (E) - [Structural Formula ^{1-4]: 1 H NMR δ =} 2.00 (s, 6H), 2.07 (s, 6H), 2.25 (s, 6H), 3.77 (s, 6H), 3.79 ( (m, 2H), 6.29 (d, J = 11.2 Hz, 2H), 6.41 (d, J = 15.2 Hz, 2H), 3.92 (s, 6H) ), 6.56 (d, J = 16.4 Hz, 2H), 6.60-6.72 (m, 2H), 6.69 (dd, J = 15.2, 11.2 Hz, 2H), 6.86 (d, J = 16.4 Hz, 2H) ppm; ^{13 C} NMR? = 12.6, 12.8, 13.0, 60.5, 60.7, 61.2, 61.3, 121.5, 125.0, 125.1, 126.6, 130.2, 132.8, 132.9, 136.2, 136.6, 138.1, 138.6, 144.9, 145.7, 148.0, 148.1 ppm; UV (CH ₂ Cl ₂ , c = 2.39 × 10 ^-5 )? (?) = 452 (36,700), 474 (37,600) nm; IR (KBr) 2989, 2937, 2855, 2833, 1729, 1677, 1565, 1469, 1409, 1349, 1267, 1193, 1111, 1081, 1066, 1036, 1014, 969, 887, 753 cm ^-1 ; HRMS (FAB) calcd for C ₄₄ H ₅₆ O ₈ 712.3975, found 712.3967.

Example 11 A compound represented by the structural formula 1-5

4,4 '- (3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis (N, N-diphenylaniline) .

(106 mg, 0.196 mmol) and 4- (diphenylamino) benzaldehyde (268 mg, 0.98 mmol) of the structural formula 2 were dissolved in methanol (30 mL) and toluene (30 mL), followed by KOMe (344 mg, 4.90 mmol). The mixture was reacted at 110 ° C for 12 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain a carotene compound (67 mg, 0.086 mmol, all- ( E )) Was obtained in a yield of 44%. Data for all- (E) - [Structural Formula ^{1-5]: 1 H NMR δ =} 1.99 (s, 6H), 2.04 (s, 6H), 6.25-6.32 (m, 2H), 6.31 (d, J = 11.6 Hz, 2H), 6.40 (d , J = 15.2 Hz, 2H), 6.54 (d, J = 15.6 Hz, 2H), 6.62-6.69 (m, 2H), 6.68 (dd, J = 15.2, 11.6 Hz, 2H ), 6.80 (d, J = 15.6 Hz, 2H), 7.00-7.34 (m, 28H) ppm; ¹³ C NMR? = 12.8, 12.9, 122.9, 123.6, 124.4, 125.1, 126.0, 127.1, 129.2, 130.2, 132.0, 132.1, 132.5, 132.9, 135.8, 136.6, 137.8, 146.9, 147.5 ppm; IR (KBr) 3034, 2922, 2855, 1737, 1588, 1491, 1327, 1282, 1178, 962, 895, 835, 753, 693 cm ^-1 ; HRMS (FAB) calcd for C ₅₈ H ₅₄ N ₂ 778.4287, found 778.4297.

Example 12. A compound represented by the formula [1-6]

(3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis (4,1-phenylene)) bis (methylsulfane ).

(605 mg, 1.12 mmol) and 4- (methylthio) benzaldehyde (852 mg, 5.6 mmol) of the structural formula 2 were dissolved in methanol (30 mL) and toluene 30 mL), followed by KOMe (1.96 g, 27.98 mmol). The mixture was reacted at 110 ° C for 12 hours under an argon atmosphere and then purified by recrystallization using methanol to obtain 251 mg of a carotene compound represented by Structural Formula 1-6 (0.468 mmol, 9- ( Z )) Was obtained in a yield of 42%. Data for 9- (Z) - [Structural Formula ^{1-6]: 1 H NMR δ =} 1.99 (s, 3H), 2.03 (s, 3H), 2.04 (s, 6H), 2.49 (s, 3H), 2.50 ( s, 3H), 6.16 (d , J = 11.6 Hz, 1H), 6.26-6.36 (m, 2H), 6.33 (d, J = 11.6 Hz, 1H), 6.35 (d, J = 14.8 Hz, 1H), 6.42 (d, J = 14.8, 1H), 6.53 (d, J = 14.8 Hz, 1H), 6.57 (d, J = 14.8 Hz, 1H), 6.60-6.70 (m, 2H), 6.67 (dd, J = 14.8, 11.6 Hz, 1H, calcd ), 6.86 (d, J = 14.8 Hz, 1H), 6.88 (dd, J = 14.8, 11.6 Hz, 1H, calcd), 7.20 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.0 Hz , 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 14.8 Hz, 1H, calcd), 7.40 (d, J = 8.0 Hz, 2H) ppm ; ¹³ C NMR? = 12.8, 12.9, 12.9, 15.8, 15.8, 20.8, 123.5, 124.9, 125.0, 126.6, 126.6, 126.7, 126.7, 126.8, 126.8, 126.8, 126.8, 126.9, 128.5, 130.2, 130.2, 130.3, 131.4 , 132.9, 133.0, 133.1, 133.8, 134.7, 134.8, 135.5, 136.5, 136.5, 137.2, 137.5, 137.6, 138.2 ppm; IR (KBr) 2975, 2932, 1750, 1442, 1383, 1231, 1064, 972, 902, 778 cm ^-1 ; UV (CH ₂ Cl ₂ , c = 8.67 × 10 ^-6 )? (?) = 462 (53,000), 485 (60,000), 517 (45,000) nm; HRMS (FAB) calcd for C ₃₆ H ₄₀ S ₂ 536.2571, found 536.2581.

Example 13 A compound represented by the structural formula 1-7

((3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis (3,5-dimethyl- phenylene)) bis (methylsulfane).

(800 mg, 1.48 mmol) and 2,6-dimethyl-4- (methylthio) benzaldehyde (934 mg, 5.18 mmol) of the structural formula 2 were dissolved in methanol 30 mL) and toluene (30 mL), followed by KOMe (2.07 g, 29.60 mmol). The mixture was reacted at 110 ° C for 12 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain a carotene compound (196 mg, 0.488 mmol, all- ( E )) Was obtained in a yield of 33%. Data for all- (E) - [Structural Formula ^{1-7]: 1 H-NMR δ} = 1.99 (s, 6H), 2.07 (s, 6H), 2.31 (s, 12H), 2.47 (s, 6H), 6.23 (d, J = 11.6 Hz, 2H), 6.23-6.33 (m, 2H), 6.37 (d, J = 16.4 Hz, 2H), 6.40 (d, J = 14.8 Hz, 2H), 6.54 (d, J = 16.4 Hz, 2H), 6.60-6.70 (m, 2H), 6.68 (dd, J = 14.8, 11.6 Hz, 2H), 6.96 (s, 4H) ppm; ¹³ C-NMR? = 12.4, 12.5, 15.6, 20.9, 20.9, 124.5, 124.8, 125.8, 129.9, 132.1, 132.6, 134.1, 135.2, 135.5, 136.3, 136.4, 137.8, 138.5 ppm; UV (CH ₂ Cl ₂ , c = 3.35 × 10 ^-5 )? (?) = 472 (128,000) nm; IR (KBr) 3032, 2932, 1744, 1666, 1589, 1551, 1451, 1366, 1219, 964, 772 cm ^-1 ; HRMS (FAB) calcd for C ₄₀ H ₄₈ S ₂ 592.3197, found 592.3196.

Example 14. A compound represented by the structural formula 1-8

4,4 '- (3,7,12,16-tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) dibenzonitrile.

(150 mg, 0.28 mmol) and 4-formylbenzonitrile (182 mg, 1.39 mmol) of the structural formula 2 were dissolved in methanol (30 mL) and toluene (30 mL) mL) and KOMe (486 mg, 6.94 mmol) is added. The mixture was reacted at 110 ° C for 12 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain a carotene compound (42 mg, 0.084 mmol, all- ( E )) Was obtained in a yield of 30%. Data for all- (E) - [Structural Formula ^{1-8]: 1 H NMR δ =} 2.05 (s, 6H), 2.12 (s, 6H), 6.28-6.340 (m, 2H), 6.42 (d, J = 11.6 Hz, 2H), 6.47 (d , J = 15.2 Hz, 2H), 6.55 (d, J = 15.6 Hz, 2H), 6.64-6.72 (m, 2H), 6.68 (dd, J = 15.2, 11.6 Hz, 2H ), 6.99 (d, J = 15.6 Hz, 2H), 7.46-7.54 (m, 4H), 7.54-7.64 (m, 4H) ppm.

Example 15. A compound represented by the structural formula 1-9

2,2 '- (3,7,12,16-tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis (methylbenzene).

(154 mg, 0.28 mmol) and o -tolualdehyde (171 mg, 1.42 mmol) in the same manner as in Example 7 were dissolved in methanol (30 mL) and toluene (30 mL) After dissolving, add KOMe (499 mg, 7.12 mmol). The mixture was reacted at 110 ° C for 12 hours under an argon atmosphere and purified by recrystallization using methanol to obtain a carotene compound (57 mg, 0.12 mmol, all- ( E )) Was obtained in a yield of 43%. Data for all- (E) - [Structural Formula ^{1-9]: 1 H NMR δ =} 2.00 (s, 6H), 2.07 (s, 6H), 2.39 (s, 6H), 6.25-6.35 (m, 2H), 6.34 (d, J = 11.6 Hz , 2H), 6.42 (d, J = 14.8 Hz, 2H), 6.62-6.71 (m, 2H), 6.69 (dd, J = 14.8, 11.6 Hz, 2H), 6.78 (d J = 16.0 Hz, 2H), 6.82 (d, J = 16.0 Hz, 2H), 7.10-7.21 (m, 6H), 7.53 (d, J = 8.0 Hz, 4H) ppm; ¹³ C NMR? = 12.8, 13.0, 19.9, 124.9, 124.9, 125.0, 126.1, 127.1, 130.3, 130.4, 133.1, 133.1, 134.8, 135.5, 135.8, 136.6, 136.6, 138.2 ppm.

Example 16. A compound represented by the formula [1-10]

4,4 '- (3,7,12,16-tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) bis (methoxybenzene).

(300 mg, 0.27 mmol) and p -anisylaldehyde (180 mg, 1.32 mmol) in the same manner as in Example 7 were dissolved in methanol (30 mL) and toluene (30 mL) Followed by KOMe (464 mg, 6.61 mmol). The mixture was reacted at 110 ° C for 24 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain a carotene compound (39 mg, 0.77 mmol, 9- ( Z )) Was obtained in a yield of 29%. Data for 9- (Z) - [Structural Formula ^{1-10]: 1 H NMR δ =} 1.99 (s, 3H), 2.02 (s, 3H), 2.04 (s, 6H), 3.83 (s, 6H), 6.13 ( d, J = 10.4 Hz, 1H ), 6.22-6.35 (m, 2H), 6.31 (d, J = 11.2 Hz, 1H), 6.34 (d, J = 14.0 Hz, 1H), 6.40 (d, J = 14.8 , 1H), 6.54 (d, J = 15.2 Hz, 1H), 6.58 (d, J = 16.0 Hz, 1H), 6.59-6.73 (m, 2H), 6.67 (dd, J = 14.8, 11.2 Hz, 1H, calcd), 6.78 (d, J = 15.2 Hz, 1H), 6.87 (d, J = 8.0 Hz, 2H), 6.89 (d, J = 8.0 Hz, 2H), 6.92 (dd, J = 14.0, 10.4 Hz, 1H, cacld), 7.32 (d , J = 16.0 Hz, 1H), 7.37 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H) ppm.

Example 17 A compound represented by the structural formula 1-11

3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) dibenzene.

Tetraethyl bis (phosphonate) (155 mg, 0.287 mmol) and benzaldehyde (152 mg, 1.43 mmol) in the same manner as in Example 7 were dissolved in methanol (30 mL) and toluene (30 mL) Add KOMe (503 g, 7.18 mmol). The mixture was reacted at 110 DEG C for 12 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain a carotene compound (68 mg, 0.152 mmol) represented by the structural formula 1-11 as red solid in 53% Yield. &Lt; / RTI > The solid obtained from the solution extracted with diethyl ether in the purification of the reaction product was recrystallized from methanol to obtain 9- ( Z ) -carotene. A small amount of substance which was not dissolved in diethyl ether but suspended in the aqueous solution layer was dissolved in CH ₂ Cl _2, and the resulting solid was recrystallized from methanol to obtain all- ( E ) -carotene.

Data for 9- (Z) - [Structural Formula ^{1-11]: 1 H NMR δ =} 2.00 (s, 3H), 2.03 (s, 3H), 2.05 (s, 6H), 6.18 (d, J = 11.2 Hz, 1H), 6.26-6.34 (m, 2H ), 6.35 (d, J = 11.2 Hz, 1H), 6.35 (d, J = 14.8 Hz, 1H), 6.42 (d, J = 14.8 Hz, 1H), 6.58 ( d, J = 15.6 Hz, 1H ), 6.62 (d, J = 15.6 Hz, 1H), 6.62-6.70 (m, 2H), 6.68 (dd, J = 14.8, 11.2 Hz, 1H), 6.89 (dd, J = 14.8, 11.2 Hz, 1H; H 11), 6.90 (d, J = 15.6 Hz, 1H), 7.17-7.26 (m, 2H), 7.29-7.37 (m, 4H), 7.41-7.50 (m, 4H) , 7.44 (d, J = 15.6 Hz, 1H; H 8) ppm; ¹³ C NMR? = 12.8, 12.9, 12.9, 20.9, 123.6, 125.0, 125.5, 126.3, 126.5, 127.1, 127.4, 127.5, 128.6, 128.7, 129.1, 130.2, 130.3, 131.6, 132.9, 133.1, 133.2, 133.6, 133.9 , 135.5, 136.5, 136.5, 136.6, 137.5, 137.8, 138.3 ppm; UV (CH ₂ Cl ₂ , c = 8.43 × 10 ^-4 )? (?) = 451 (84,400), 476 (110,900), 508 (92,800) nm; IR (KBr) 3027, 2922, 2855, 1729, 1595, 1491, 1446, 1394, 1372, 1215, 1029, 962, 753, 693 cm ^-1 ; HRMS (FAB) calcd for C ₃₄ H ₃₆ 444.2817, found 444.2814.

Data for all- (E) - [Structural Formula ^{1-11]: 1 H NMR δ =} 2.00 (s, 6H), 2.05 (s, 6H), 6.25-6.36 (m, 2H), 6.35 (d, J = 11.6 Hz, 2H), 6.43 (d , J = 14.8 Hz, 2H), 6.59 (d, J = 16.0 Hz, 2H), 6.61-6.72 (m, 2H), 6.68 (dd, J = 14.8, 11.6 Hz, 2H ), 6.91 (d, J = 16.0 Hz, 2H), 7.17-67.24 (m, 2H), 7.28-7.36 (m, 4H), 7.40-7.47 (m, 4H) ppm; ¹³ C NMR? = 12.8, 12.9, 125.0, 126.3, 127.2, 127.4, 128.6, 130.3, 133.1, 133.2, 133.6, 135.5, 136.6, 137.8, 138.2 ppm; UV (CH ₂ Cl ₂ , c = 1.12 × 10 ^-5 )? (?) = 454 (57,800), 480 (81,900), 513 (72,900) nm; IR (KBr) 3027, 2945, 2915, 1722, 1662, 1595, 1573, 1551, 1491, 1446, 1334, 962, 745, 686 cm ^-1 ; HRMS (FAB) calcd for C ₃₄ H ₃₆ 444.2817, found 444.2816.

Example 18 A compound represented by the formula [1-12]

2,2 '- (3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) dinaphthalene.

(653 mg, 1.21 mmol) and 2-naphthalaldehyde (943 mg, 6.04 mmol) in the same manner as in Example 7 were dissolved in methanol (30 mL) and toluene (30 mL) Followed by KOMe (2.12 g, 30.2 mmol). The mixture was reacted at 110 ° C for 12 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain a carotene compound represented by the structural formula 1-12 (258 mg, 0.474 mmol, 9- ( Z )) Was obtained in a yield of 39%. Data for 9- (Z) - [Structural Formula ^{1-12]: 1 H-NMR δ} = 2.01 (s, 3H), 2.06 (s, 3H), 2.10 (s, 3H), 2.11 (s, 3H), 6.21 (d, J = 10.8 Hz, 1H), 6.28-6.35 (m, 2H), 6.38 (d, J = 14.4 Hz, 1H), 6.40 (d, J = 11.6 Hz, 1H), 6.45 (d, J = 14.8, 1H), 6.63-6.74 (m , 2H), 6.68 (dd, J = 14.4, 10.8 Hz, 1H, calcd), 6.76 (d, J = 15.6 Hz, 1H), 6.79 (d, J = 15.6 Hz , 1H), 6.95 (dd, J = 14.8, 11.6 Hz, 1H), 7.04 (d, J = 15.6 Hz, 1H), 7.39-7.49 (m, 4H), 7.57 (d, J = 15.6 Hz, 1H) , 7.64-7.84 (m, 10H) ppm; ¹³ C NMR? = 12.8, 12.9, 13.0, 20.9, 123.6, 123.6, 125.0, 125.7, 125.8, 126.2, 126.3, 126.3, 126.6, 127.5, 127.7, 127.7, 127.9, 128.0, 128.2, 128.3, 129.2, , 130.4, 131.8, 132.6, 133.0, 133.0, 133.4, 133.6, 133.8, 133.8, 133.9, 134.0, 135.3, 135.4, 135.6, 136.6, 136.6, 137.7, 137.7, 138.4 ppm; IR (KBr) 3053, 3023, 2922, 2855, 1737, 1625, 1595, 1439, 1368, 1241, 1129, 1047, 1025, 962, 895, 861, 816, 745, 619 cm ^-1 ; UV (CH ₂ Cl ₂ , c = 7.02 10 ^-5 )? (?) = 458 (14,100), 484 (13,800), 517 (10,100) nm; HRMS (FAB) calcd for C ₄₂ H ₄₀ 544.3130, found 544.3132.

Example 19. A compound represented by the formula [1-13]

2,2 '- (3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) difuran.

(480 mg, 0.89 mmol) and 2-furaldehyde (427 mg, 4.44 mmol) in the same manner as in Example 7 were dissolved in methanol (30 mL) and toluene (30 mL) Followed by KOMe (1.56 g, 22.2 mmol). The mixture was reacted at 110 ° C for 12 hours under an argon atmosphere, and then purified by recrystallization using methanol to obtain a carotene compound (152 mg, 0.358 mmol, all- ( E )) Was obtained in a yield of 40%. Data for all- (E) - [Structural Formula ^{1-13]: 1 H NMR δ =} 1.99 (s, 12H), 6.25-6.35 (m, 2H), 6.27 (d, J = 3.2 Hz, 2H), 6.33 ( d, J = 11.6 Hz, 2H ), 6.38 (d, J = 14.8 Hz, 2H), 6.40 (dd, J = 3.2, 1.6 Hz, 2H), 6.41 (d, J = 16.0 Hz, 2H), 6.61- 6.70 (m, 2H), 6.66 (dd, J = 14.8,11.6 Hz, 2H), 6.82 (d, J = 16.0 Hz, 2H), 7.36 (d, J = 1.6 Hz, 2H) ppm; ¹³ C NMR? = 12.6, 12.8, 108.0, 111.7, 115.3, 125.0, 130.3, 132.2, 133.1, 133.2, 135.1, 136.6, 138.2, 141.9, 153.9 ppm; UV (CH ₂ Cl ₂ , c = 1.17 x 10 ^-5 )? (?) = 460 (65,400), 487 (88,400), 522 (75,000) nm; IR (KBr) 3146, 3116, 3027, 2982, 2919, 2855, 1733, 1718, 1703, 1674, 1655, 1603, 1551, 1480, 1439, 1390, 1379, 1252, 1219, 1152, 1073, 928, 883, 753, 734 cm < ^{-1 &} gt ;; _{HRMS (FAB) calcd for C 30} H 32 O 2 424.2402, found 424.2405.

Example 20. A compound represented by the formula [1-14]

2,2 '- (3,7,12,16-Tetramethyloctadeca-1,3,5,7,9,11,13,15,17-nonaene-1,18-diyl) dithiophene.

(92 mg, 0.17 mmol) and 2-thiophenecarboxaldehyde (95 mg, 0.85 mmol) of the structural formula 2 were dissolved in methanol (30 mL) and toluene 30 mL) and KOMe (297 mg, 4.23 mmol) was added. The mixture was reacted at 110 DEG C for 12 hours under an argon atmosphere and purified by recrystallization using methanol to obtain a carotene compound represented by the structural formula 1-14 (51 mg, 0.11 mmol, 9- ( Z )) Was obtained in a yield of 66%. Data for 9- (Z) - [Structural Formula ^{1-14]: 1 H NMR δ =} 1.99 (s, 3H), 2.01 (s, 3H), 2.02 (s, 6H), 6.14 (d, J = 11.6 Hz, 1H), 6.26-6.34 (m, 2H ), 6.31 (d, J = 11.6 Hz, 1H), 6.34 (d, J = 14.8 Hz, 1H), 6.41 (d, J = 14.8 Hz, 1H), 6.60- 6.70 (m, 2H), 6.64 (d, J = 15.6 Hz, 1H), 6.66 (dd, J = 14.8, 11.6 Hz, 1H, calcd), 6.70 (d, J = 16.0 Hz, 1H), 6.74 (d , J = 16.0 Hz, 1H) , 6.84 (dd, J = 14.8, 11.6 Hz, 1H), 6.96-7.01 (m, 3H), 7.03 (d, J = 3.2 Hz, 1H), 7.14 (d, J = 4.8 Hz, 1H), 7.18 (d, J = 5.2 Hz, 1H), 7.24 (d, J = 15.6 Hz, 1H) ppm; ¹³ C-NMR? = 12.7, 12.8, 12.9, 20.7, 120.5, 122.1, 122.5, 123.6, 123.9, 124.3, 124.9, 125.4, 125.9, 127.6, 127.7, 130.2, 130.3, 131.4, 132.9, 133.0, 133.1, 133.4, 133.5, 135.0, 136.5, 136.5, 137.5, 138.3, 143.5, 143.7 ppm; IR (KBr) 2922, 2855, 1737, 1461, 1372, 1245, 1163, 1021, 962, 850, 835, 805, 753, 693 cm ^-1 ; UV (CH ₂ Cl ₂ , c = 8.45 × 10 ^-5 )? (?) = 464 (8,380), 489 (11,000), 522 (9,050) nm; HRMS (FAB) calcd for C ₃₀ H ₃₂ S ₂ 456.1945, found 456.1945.

Claims

(2,6,11,15-tetramethylhexadeca-2,4,6,8,10,12,14-heptaen-1,16-diyl) bis (phosphonate ).

[Structural formula 2]
Diethyl (4- (benzo [ d ] thiazole-2-ylsulfonyl) -2-methyl-2-butene-1-yl) phosphonate represented by the following structural formula 5.

[Structural Formula 5]
(a) preparing a chlorohydrin compound represented by the following structural formula D from isoprene;

(b) brominating an allylic alcohol of the compound represented by the following structural formula D to produce an allyl-ylide halide compound represented by the following formula (E);

(c) reacting an allyl halide compound represented by the formula (E) with 2-mercaptobenzothiazole to prepare a chloroallylic sulfide compound represented by the formula (F);

(d) preparing a chloroallylic sulfone compound represented by the following formula (G) by oxidation reaction of a chloroallylic sulfide compound represented by the following formula (F); And

(e) producing a diethylphosphonate group by Arbuzov reaction of allylic chloride of the compound represented by the formula (G) with triethylphosphite [P (OEt) 3 ] A process for producing diethyl (4- (benzo [ d ] thiazole-2-ylsulfonyl) -2-methyl-2-buten-1-yl) phosphonate represented by the following structural formula 5.

[Structural formula D]

[Structural formula E]

[Structural formula F]

[Structural formula G]

[Structural Formula 5]
The method of claim 3,

Wherein the allyl halide compound represented by the structural formula E and the 2-mercaptobenzothiazole are reacted in an equivalent ratio of 1: 1 in the step (c) [ d ] thiazole-2-ylsulfonyl) -2-methyl-2-buten-1-yl) phosphonate.
(4- (benzo [ d ] thiazole-2-ylsulfonyl) -2-methyl-2-buten-1-yl) phosphonate represented by the following structural formula 5 and 2,7 -Dimethyl-2,4,6-octatriendial are reacted to obtain tetraethyl (2,6,11,15-tetramethylhexadeca-2,4,6,8,10,12, 14-heptaen-1,16-diyl) bis (phosphonate).

[Structural Formula 5]

[Structural Formula 4]

[Structural formula 2]
The method of claim 5,

(Benzo [ d ] thiazole-2-ylsulfonyl) -2-methyl-2-buten-1-yl) phosphonate represented by the structural formula 5 and 2,7 (2,6,11,15-tetramethylhexadec-2-ene) represented by the structural formula 2, which is reacted at an equivalent ratio of 2: 1 to dimethyl-2,4,6- Heptaen-1,16-diyl) bis (phosphonate).
Reacting a C 20 polyenbis (phosphonate) compound represented by the following structural formula 2 with an aldehyde compound represented by the following structural formula A to produce a carotene compound represented by the following structural formula 1.

[Structural formula 2]

[Structural Formula A]

In Formula A above, R may be selected from the group consisting of alkyl, aryl, aralkyl, and heteroaryl having 5 to 20 carbon atoms.

[Structural formula 1]

In Formula 1, R may be selected from the group consisting of alkyl, aryl, aralkyl, and heteroaryl having 5 to 20 carbon atoms.
The method of claim 7,

Wherein the carotene compound represented by Formula 1 is prepared by reacting a C 20 polyenbis (phosphonate) compound represented by Formula 2 with an aldehyde compound represented by Formula A in an equivalent ratio of 1: 2 Way.
The method of claim 7,

In the structural formula A and the structural formula 1, R is
,
,
,

,
,
,
,

,
,
,
,
,

And
&Lt; RTI ID = 0.0 > carotene < / RTI >
A carotene compound represented by the following structural formula 1-1.

[Structural formula 1-1]
A carotene compound represented by the following structural formula (1-2).

[Structural formula 1-2]
A carotene compound represented by the following structural formula (1-3).

[Structural Formula 1-3]
A carotene compound represented by the following structural formula 1-4.

[Structural Formula 1-4]
A carotene compound represented by the following structural formula (1-5).

[Structural Formula 1-5]
A carotene compound represented by the following structural formula 1-6.

[Structural formula 1-6]
A carotene compound represented by Structural Formula 1-7 below.

[Structural formula 1-7]
A carotene compound represented by the following structural formula 1-8.

[Structural formula 1-8]
A carotene compound represented by the following structural formula 1-9.

[Structural formula 1-9]