KR101742022B1 - New Biaryl Compounds and Preparation method thereof by benzannulation - Google Patents

New Biaryl Compounds and Preparation method thereof by benzannulation Download PDF

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KR101742022B1
KR101742022B1 KR1020150129384A KR20150129384A KR101742022B1 KR 101742022 B1 KR101742022 B1 KR 101742022B1 KR 1020150129384 A KR1020150129384 A KR 1020150129384A KR 20150129384 A KR20150129384 A KR 20150129384A KR 101742022 B1 KR101742022 B1 KR 101742022B1
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hydroxy
allyl
carboxamide
methoxyphenyl
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영남대학교 산학협력단
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/017—Esters of hydroxy compounds having the esterified hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
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Abstract

The present invention relates to a novel biaryl compound and a process for its preparation using a benzene cyclization reaction. More particularly, the novel biaryl compound synthesized according to the process of the present invention can be easily and environmentally friendly And the biaryl compound can be widely used for synthesis of natural products, organic functional materials, electronic materials, dyes, and perfume production.

Description

TECHNICAL FIELD The present invention relates to a novel biaryl compound and a method for producing the same using a benzene cyclization reaction.

The present invention relates to novel biaryl compounds and processes for their preparation using benzene cyclization.

Biaryl compounds are widely found in nature. Compounds with such skeletons show various physiological and pharmacological activities. These skeletal compounds are also widely used as intermediates in the synthesis of pharmaceuticals and natural products. Especially, these skeletons are widely used for the synthesis of functional electronic material compounds.

Reports of several aryl-aryl bond formation are known, and a typical cross-linking coupling reaction (Suzuki, Stille, Hiyama, etc.) using a transition metal catalyst among them is carried out by reaction of an aryl halide with an aryl metal to form an aryl- It is a useful method to form. Recently, the transition metal catalyst C-H arylation and the oxidative cross-linking reaction of arene have been reported as important crosslinking coupling strategies for aryl-aryl bond formation. While this direct arylation has the advantage of reducing many synthetic processes, it is expensive and environmentally friendly.

Therefore, there is a need for a process for producing a biaryl compound more easily without using an expensive transition metal.

Korea Patent Publication No. 2013-0119729

It is an object of the present invention to provide novel biaryl compounds.

It is an object of the present invention to provide a novel method for producing a biaryl compound using a benzene ring-forming reaction.

In order to accomplish the above object, the present invention provides a biaryl compound represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

A is selected from phenyl, furan-2-yl or anthracen-9-yl,

R 1 is C1 to C4 alkyl, alkoxy C1 to C4, -OCH 2 CH = CH 2 , PhNH-, 4-MeOC 6 H 4 NH-, 4-MeC 6 H 4 NH-, 2-MeOC 6 H 4 NH-, 2-MeC 6 H 4 NH-, 4-ClC 6 H 4 NH- , and 2-ClC 6 is selected from the group consisting of H 4 NH-,

R 2 and R 3 are the same or different and are selected from the group consisting of hydrogen, C 1 to C 4 alkyl, C 1 to C 4 alkoxy and halogen,

Or when R 4 is a 4-mil, 3- (4-methoxyphenyl) allyl-3- (4-fluorophenyl) allyl, 4- (3-phenyl-allyl -1,3-d 2), 2- chloro-benzyl , 2-bromobenzyl, 3- (furan-2-yl) allyl, 3- (anthracen-9-yl) allyl and 3-phenylpropyl.

The present invention also provides a method for producing a biaryl compound, which comprises refluxing a compound represented by the formula (1) and a compound represented by the formula (2) in the presence of Cs 2 CO 3 as a catalyst and toluene as a solvent, do:

[Reaction Scheme 1]

Figure 112015088834720-pat00002

In the above Reaction Scheme 1,

R 1 is C1 to C4 alkyl, alkoxy C1 to C4, -OCH 2 CH = CH 2 , PhNH-, 4-MeOC 6 H 4 NH-, 4-MeC 6 H 4 NH-, 2-MeOC 6 H 4 NH-, 2-MeC 6 H 4 NH-, 4-ClC 6 H 4 NH- , and 2-ClC 6 is selected from the group consisting of H 4 NH-,

R 2 and R 3 are the same or different and can be selected from the group consisting of hydrogen, C 1 to C 4 alkyl, C 1 to C 4 alkoxy and halogen.

The novel biaryl compound synthesized according to the preparation method of the present invention has an advantage that it can be synthesized more easily, environmentally friendly and efficiently without using a transition metal. Particularly, the biaryl compound is useful for synthesis of natural products, Materials, dyes, and perfumes.

The present inventors have conducted research and development on a method for easily synthesizing a biaryl compound, which is an important substance exhibiting various physiological activities, in an easier, environmentally friendly, and efficient manner, and have found that a beta-ketoester, The present invention has been completed on the discovery that various types of novel biaryl compounds can be synthesized by reacting cinnamaldehyde or arylaldehyde with diketone in the presence of a specific base, Cs 2 CO 3 , as a catalyst, through a benzene cyclization reaction.

The present invention provides a biaryl compound represented by the following Formula 1:

[Chemical Formula 1]

Figure 112015088834720-pat00003

In Formula 1, A is phenyl, furan, or is selected from 2-yl-anthracene-9-yl, R 1 is C1 to C4 alkyl, alkoxy C1 to C4, -OCH 2 CH = CH 2, PhNH-, 4-MeOC 6 H 4 NH-, 4-MeC 6 H 4 NH-, 2-MeOC 6 H 4 NH-, 2-MeC 6 H 4 NH-, 4-ClC 6 H 4 NH- , and 2-ClC 6 H 4 NH-, wherein R 2 and R 3 are each the same or different and are selected from the group consisting of hydrogen, C 1 to C 4 alkyl, C 1 to C 4 alkoxy and halogen, R 4 is selected from the group consisting of 4- 3- (4-methoxyphenyl) allyl-3- (4-fluorophenyl) allyl, 4- (3-phenyl-allyl -1,3-d 2), 2- chlorobenzyl, 2-bromobenzyl, May be selected from the group consisting of 3- (furan-2-yl) allyl, 3- (anthracen-9-yl) allyl and 3-phenylpropyl.

More specifically, the biaryl compounds include methyl 4-cinnamoylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -methyl 3-hydroxy-4'-methoxy- (E) -methyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybis Phenyl-2-carboxylate, ethyl 4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -ethyl 3-hydroxy-4'- (E) -ethyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl- Cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -allyl 4'-fluoro-4- (3- (4- fluorophenyl) (E) -benzyl 3-hydroxy-2'-methoxy-4- (3- (2-methoxyphenyl) allyl) biphenyl-2-carboxylate 4-cinnamylmethyl-3-hydroxy-N- (E) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy-N-phenylbiphenyl-2-carboxamide (E) -3-hydroxy-4'-methoxy-N- (4-methoxyphenyl) 4- (3- (4-methoxyphenyl) allyl) biphenyl-2-carboxamide, (E) (4-methoxyphenyl) biphenyl-2-carboxamide, 4-cinnamoyl-3-hydroxy-Np-tolyl biphenyl- (E) -4 ' -fluoro-biphenyl-2-carboxamide, 3-hydroxy-N-tolylbiphenyl-2-carboxamide, 4- cinnamylmethyl-3-hydroxy-N-tolylbiphenyl- Carboxamide, (E) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy- (E) -N- (4-chlorophenyl) - (4-chlorophenyl) -4-cinnamylmethyl 3-hydroxybiphenyl-2-carboxamide, (E) -N- (4-chlorophenyl) -4'- (3-hydroxy-4'-methoxy- Fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl-2-carboxamide, (E) 2-carboxamide, N- (2-chlorophenyl) -4-cinnamylmethyl-3-hydroxybiphenyl-2 -Carboxamide, (E) -N- (2-chlorophenyl) -3-hydroxy-4'-methoxy-4- (3- (4- methoxyphenyl) allyl) Amide, (E) -N- (2- chlorophenyl) -4'-fluoro-4- (3- (4- fluorophenyl) allyl) -3-hydroxybiphenyl- Ethan-1-one, (E) -3-hydroxy-N- (4-methoxyphenyl) ) -4- (3-phenyl-allyl -1,3-d 2) - [1,1'- biphenyl] -2-carboxamide, amide, methyl 4- (2-chlorobenzyl) -3-hydroxy-4 4-methoxybiphenyl-2-carboxylate, 4- (2-chlorobenzyl) -3-hydroxy- ) - 3-hydroxy-4'-methoxy-Np-tolylbiphenyl-2-carboxamide, 4- (2- chlorobenzyl) 2-carboxamide, (E) -methyl 6- (furan-2-yl) -3- (3- (furan-2-yl) allyl) -2-hydroxybenzoate, E) -ethyl 6- (furan-2-yl) -3- (3- (furan-2-yl) allyl) -2- hydroxybenzoate, 3- (3-furan-2-yl) allyl) -2-hydroxybenzoate, (E) (E) -methyl 6- (anthracen-9-yl) -3- (3- (anthracene-9-yl) allyl) -2-hydroxybenzamide, Hydroxybenzoate, (E) -ethyl 6- (anthracen-9-yl) Hydroxy-4- (3-phenylpropyl) biphenyl-2-carboxylate and 3-hydroxy-3- -N- (4-methoxyphenyl) -4- (3-phenylpropyl) biphenyl-2-carboxamide.

The present invention also provides a method for producing a biaryl compound, which comprises refluxing a compound represented by the formula (1) and a compound represented by the formula (2) in the presence of Cs 2 CO 3 as a catalyst and toluene as a solvent, do:

[Reaction Scheme 1]

Figure 112015088834720-pat00004

In the above scheme 1, R 1 is C1 to C4 alkyl, alkoxy C1 to C4, -OCH 2 CH = CH 2 , PhNH-, 4-MeOC 6 H 4 NH-, 4-MeC 6 H 4 NH-, 2 -MeOC 6 H 4 NH-, 2-MeC 6 H 4 NH-, 4-ClC 6 H 4 NH- and 2-ClC 6 H 4 NH-, R 2 and R 3 are each the same or different And can be selected from the group consisting of hydrogen, C1 to C4 alkyl, C1 to C4 alkoxy and halogen.

As the biaryl compound, methyl 4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -methyl 3-hydroxy-4'- (E) -methyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl-2- (E) -ethyl 3-hydroxy-4'-methoxy-4- (3- (4-methoxyphenyl) (E) -ethyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl-2-carboxylate, Cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -allyl 4'-fluoro-4- (3- (4- fluorophenyl) allyl) -3- Phenyl-2-carboxylate, (E) -benzyl 3-hydroxy-2'-methoxy-4- (3- (2- methoxyphenyl) Methyl-3-hydroxy-N-phenylbiphenyl-2-car (4-fluorophenyl) allyl) -3-hydroxy-N-phenylbiphenyl-2-carboxamide, 4- (E) -3-hydroxy-4'-methoxy-N- (4-methoxyphenyl) -4- (E) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy (E) -3-hydroxy-isoquinolin-3-ylmethyl-N-phenylcarbamoyl- 4'-fluoro-4- (3- (4-methoxyphenyl) allyl) -Np-tolylbiphenyl-2-carboxamide, 3-hydroxy-N-tolylbiphenyl-2-carboxamide, (E) -trifluorobiphenyl-2-carboxamide, -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy-N-tolylbiphenyl- -Carboxamide, N- (4-chlorophenyl) -4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxamide, (E) -N- (4-chlorophenyl) -4'-fluoro-4- (4-methoxyphenyl) (E) -N- (4-chlorophenyl) -3-hydroxy-2 ' -methoxy- Carboxamide, N- (2-chlorophenyl) -4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxamide, 4- (3- (E) -N- (2-chlorophenyl) -3-hydroxy-4'-methoxy- 4- (3- (4- methoxyphenyl) allyl) (2-chlorophenyl) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3- hydroxybiphenyl- 3-hydroxy- [1,1'-biphenyl] -2-yl) ethan-1-one.

Further, the present invention relates to a process for producing 1,3-dicarbonyl compound, aryl aldehyde and 4-methoxy cinnamaldehyde in the presence of Cs 2 CO 3 as a catalyst and toluene as a solvent, There is provided a process for preparing an aryl compound:

[Reaction Scheme 2]

Figure 112015088834720-pat00005

Wherein X is selected from O or NH and R 1 is selected from the group consisting of C 1 -C 4 alkyl, 4-MeC 6 H 4 -, and 4-ClC 6 H 4 -, R 2 is halogen Lt; / RTI >

Examples of the biaryl compound include methyl 4- (2-chlorobenzyl) -3-hydroxy-4'-methoxybiphenyl-2-carboxylate, ethyl 4- 4'-methoxy-N'-methoxybiphenyl-2-carboxylate, 4- (2-chlorobenzyl) -3-hydroxy- 2-chlorobenzyl) -N- (4-chlorophenyl) -3-hydroxy-4'-methoxybiphenyl-2-carboxamide.

The present invention also relates to a process for the preparation of a compound of formula (I) which comprises reacting a compound selected from 3- (purin-2-yl) -acrylaldehyde or 3- (anthracen-9-yl) acrylaldehyde in the presence of Cs 2 CO 3 as a catalyst and toluene as a solvent, And a 1,3-dicarbonyl compound are refluxed.

[Reaction Scheme 3]

Figure 112015088834720-pat00006

In Reaction Scheme 3, X is selected from O or NH, R 1 is C1 to C4 alkyl, -CH 2 CH = CH 2 and 4-ClC 6 H 4 - can be selected from the group consisting of.

Examples of the biaryl compound include (E) -methyl 6- (furan-2-yl) -3- (3- (furan- (Furan-2-yl) -3- (3-furan-2-yl) allyl) -2-hydroxybenzoate, (Furan-2-yl) allyl) -2- hydroxybenzoate, (E) -N- (4-chlorophenyl) (E) -methyl 6- (anthracen-9-yl) -3- (3- (anthracen-9-yl) allyl) -2-hydroxybenzoate and E) -ethyl 6- (anthracen-9-yl) -3- (3- (anthracen-9-yl) allyl) -2-hydroxybenzoate.

The present invention also relates to a process for the preparation of 4-cinnamoyl-3-hydroxybiphenyl-2-carboxylate or 4-cinnamyl-3-hydroxynaphthoate as a catalyst, in the presence of palladium- Rxy-N- (4-methoxyphenyl) biphenyl-2-carboxamide is hydrogenated.

[Reaction Scheme 4]

Figure 112015088834720-pat00007

In Scheme 4 above, R can be selected from methoxy or 4-MeOC 6 H 4 NH-.

The above-mentioned biaryl compounds include methyl 3-hydroxy-4- (3-phenylpropyl) biphenyl-2-carboxylate and 3-hydroxy-N- (4-methoxyphenyl) -4- Propyl) biphenyl-2-carboxamide. ≪ / RTI >

The present invention also provides a chromene compound represented by the following Formula 2:

(2)

In Formula 2, R 1 is C1 to C4 alkyl, alkoxy C1 to C4, -OCH 2 CH = CH 2 , PhNH-, 4-MeOC 6 H 4 NH-, 4-MeC 6 H 4 NH-, 2 -MeOC 6 H 4 NH-, 2-MeC 6 H 4 NH-, 4-ClC 6 H 4 NH- and 2-ClC 6 H 4 NH-.

As the chromene compound, methyl 2,7-diphenyl-2H-chromene-8-carboxylate or N- (4-methoxyphenyl) -2,7-diphenyl-2H-chromen- ≪ / RTI >

The present invention also relates to a process for the preparation of 4-cinnamyl-3-hydroxybiphenyl (2-methyl-4-hydroxyphenyl) -2-carboxylate or 4-cinnamyl-3-hydroxy-N- (4-methoxyphenyl) biphenyl-2-carboxamide is refluxed.

[Reaction Scheme 5]

Figure 112015088834720-pat00009

In Scheme 4 above, R can be selected from methoxy or 4-MeOC 6 H 4 NH-.

As the chromene compound, methyl 2,7-diphenyl-2H-chromene-8-carboxylate or N- (4-methoxyphenyl) -2,7-diphenyl-2H-chromen- ≪ / RTI >

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by these examples.

All experiments below were carried out in air without inert gas protection. Keto ester (1a-d), ketoamides (1e-j) and cinnamaldehyde (2a-f) were purchased from Sigma-Aldrich and pre-coated silica gel plates with fluorescence indicators from Merck (Art. 5554) was used. Flash column chromatography was performed using silica gel 9385 (Merck). Melting points were measured on a Fisher-Johns melting point micro-cover glass. And 1 H NMR analysis was recorded via a Varian VNS (300 MHz) spectrometer in CDCl 3 as a solvent chemical shift at 7.24 ppm and 13 C NMR analysis was performed using a Varian VNS (75 MHz) in CDCl 3 as a solvent chemical shift of 77.0 ppm ) Spectrophotometer. IR analysis was performed using a JASCO FTIR 5300 spectrophotometer, and HR-MS analysis was performed with Jeol JMS 700 through Korea Basic Science Research Institute.

Example 1 Synthesis of 4-cinnamyl-3-hydroxy-N-phenylbiphenyl-2-carboxamide and alkyl 4-cinnamylmethyl-3-hydroxybiphenyl- 29) Synthesis

First, methyl acetacetate (1a, 0.5 mmol) and cinnamaldehyde (2a) were reacted under various conditions as shown in Table 1 below to find the optimal conditions for the synthesis of the compounds. As a result, When the NaOMe (1.0 equiv) and K 2 CO 3 (1.0 equiv) were respectively treated, the reaction yield of the compound 3 was increased to 63 and 71%, respectively. Particularly, when Cs 2 CO 3 was used as the base such as Entry 6, Yield increased to 83%.

[Table 1]

Figure 112015088834720-pat00010

In addition, a variety of cinnamaldehyde can be reacted with beta-ketoester, beta-ketoamide or 1,3-diketone in the presence of a refluxing toluene solvent and as a catalyst in the presence of a specific base, Cs 2 CO 3, A biaryl compound was synthesized.

[Table 2]

Figure 112015088834720-pat00011

More specifically, Cs 2 CO 3 (0.5 mmol) was added to a solution of cinnamaldehyde 2a-d (1.0 mmol) and ketone ester or ketoneamide 1a-j (0.5 mmol) in toluene. Each reaction mixture was refluxed for 4-8 hours. Thereafter, the reaction solvent was evaporated under reduced pressure in a rotary evaporator to obtain a residue. The residue was purified by flash column chromatography on silica gel to obtain the desired compound.

1) methyl 4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate (3)

(143 mg, 83%) was obtained by reacting cinnamaldehyde (132 mg, 1.0 mmol) with methyl 3-oxobutanoate (58 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, ) Were synthesized.

mp 65-67 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 10.88 (1H, s), 7.38-7.15 (11H, m), 6.75 (1H, d, J = 7.8 Hz), 6.50 (1H, d, J = 15.9 Hz) , 6.46-6.37 (1H, m), 3.60 (2H, d, J = 6.0 Hz), 3.46 (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 171.7, 159.1, 142.9, 142.8, 137.5, 133.8, 131.3, 128.4, 128.1, 127.9, 127.7, 127.6, 127.0, 126.7, 126.1, 122.1, 115.7, 51.7, 53.1; IR (KBr) 3434, 3054, 1663, 1436, 1276, 970, 760, 516 cm < -1 & gt ;; HRMS m / z (M + ) calcd for C 23 H 20 O 3 : 344.1412. Found: 344.1413.

2) (E) -methyl 3-hydroxy-4'-methoxy-4- (3- (4- methoxyphenyl) allyl)

(162 mg, 1.0 mmol) and methyl 3-oxobutanoate (58 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) To obtain red liquid compound 4 (155 mg, 77%).

1 H NMR (300 MHz, CDCl 3) δ 10.82 (1H, s), 7.33-7.26 (3H, m), 7.15 (2H, d, J = 8.7 Hz), 6.90 (2H, d, J = 8.7 Hz) , 6.83 (1H, d, J = 8.4 Hz), 6.75 (1H, d, J = 7.5 Hz) s), 3.80 (3H, s), 3.59 (2H, d, J = 6.6 Hz), 3.53 (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 171.9, 159.0, 158.8, 158.5, 142.4, 135.2, 133.7, 130.6, 130.4, 129.2, 127.5, 127.2, 125.7, 122.1, 113.9, 113.0, 111.8, 55.2, 55.2, 51.7 , 33.0; IR (neat) 3465, 2924, 1662, 1608, 1513, 1438, 1246, 1033, 821, 516 cm -1 ; HRMS m / z (M +) calcd for C 25 H 24 O 5: 404.1624. Found: 404.1622.

3) (E) -methyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl-

Cs 2 CO 3 (163 mg, 0.5 mmol) (E) -3- ( 4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and methyl 3-oxo-butanoate (58 mg, 0.5 mmol) in the presence To obtain a solid compound 5 (148 mg, 78%).

mp 70-72 [deg.] C; 1 H NMR (300 MHz, CDCl 3 )? 10.98 (1H, s), 7.34-7.29 (3H, m), 7.19-7.13 (2H, m), 7.06-6.93 J = 7.5 Hz), 6.45 (1H, d, J = 15.9 Hz), 6.37-6.27 (1H, m), 3.58 (2H, d, J = 6.6 Hz), 3.5 (3H, s); 13 C NMR (75 MHz, CDCl 3 ) δ 171.6, 159.3, 141.8, 138.9, 133.8, 130.0, 129.7, 129.6, 127.9, 127.6, 127.5, 122.1, 115.4, 115.1, 114.6, 114.3, 111.7, 51.8, 33.1; IR (KBr) 3410, 3039, 1664, 1605, 1511, 1434, 1227, 1153, 820, 764 cm -1 ; HRMS m / z (M + ) calcd for C 23 H 18 F 2 O 3 : 380.1224. Found: 380.1227.

4) Ethyl 4-cinnamoyl-3-hydroxybiphenyl-2-carboxylate (6)

(132 mg, 1.0 mmol) and β-ethyl-3-oxobutanoate (65 mg, 0.5 mmol) were reacted in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) mg, 79%).

1 H NMR (300 MHz, CDCl 3) δ 11.01 (1H, s), 7.31-7.12 (11H, m), 6.67 (1H, d, J = 7.8), 6.46-6.32 (2H, m), 3.89 (2H , q, J = 7.2 Hz), 3.54 (2H, d, J = 6.6 Hz), 0.66 (3H, t, J = 7.2 Hz); 13 C NMR (75 MHz, CDCl 3) δ 171.3, 161.0, 159.2, 143.1, 143.0, 137.5, 133.6, 131.2, 128.4, 128.2, 127.9, 127.5, 127.0, 126.6, 126.1, 121.9, 111.8, 61.0, 33.1, 12.9 ; IR (neat) 3394, 2989, 1675, 1607, 1518, 1224, 1157, 1010, 825, 595 cm < -1 & gt ;; HRMS m / z (M +) aldd for C 24 H 22 O 3 : 358.1569. Found: 358.1568.

5) (E) -Ethyl 3-hydroxy-4'-methoxy-4- (3- (4- methoxyphenyl) allyl)

(E) -3- (4-methoxyphenyl) acrylaldehyde (162 mg, 1.0 mmol) and ethyl-3-oxobutanoate (65 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) ) Was reacted to synthesize a yellow liquid compound 7 (148 mg, 71%).

1 H NMR (300 MHz, CDCl 3) δ 10.98 (1H, s), 7.30 (3H, d, J = 8.1 Hz), 7.15-7.12 (2H, m), 6.89-6.80 (4H, m), 6.73 ( (1H, d, J = 7.8 Hz), 6.44 (1H, d, J = 15.9 Hz), 6.32-6.22 3.78 (3H, s), 3.57 (2H, d, J = 6.6 Hz), 0.82 (3H, t, J = 7.2 Hz); 13 C NMR (75 MHz, CDCl 3) δ 171.4, 159.1, 158.8, 158.6, 142.5, 135.6, 133.5, 130.6, 130.4, 129.5, 127.6, 127.2, 125.8, 122.0, 113.9, 113.0, 112.0, 61.0, 55.3, 55.2 , 33.0, 13.2; IR (neat) 3363, 2924, 1650, 1607, 1246, 1175, 1031, 825 cm < -1 & gt ;; HRMS m / z (M + ) calcd for C 26 H 26 O 5 : 418.1780. Found: 418.1781.

6) (E) -Ethyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl-

Cs 2 CO 3 (163 mg, 0.5 mmol) (E) -3- ( 4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and ethyl 3-oxo-butanoate (65 mg, 0.5 mmol) in the presence To obtain a yellow liquid compound 8 (159 mg, 81%).

1 H NMR (300 MHz, CDCl 3) δ 11.17 (1H, s), 7.24-7.29 (3H, m), 7.19-7.14 (2H, m), 7.06-6.93 (4H, m), 6.71 (1H, d (2H, q, J = 7.2 Hz), 3.59 (2H, d, J = 6.6 Hz, J = 7.8 Hz), 6.56 (1H, d, J = 17.3 Hz), 6.38-6.28 ), 0.82 (3H, t, J = 7.2 Hz); 13 C NMR (75 MHz, CDCl 3) δ 171.1, 159.5, 141.9, 133.6, 130.0, 129.7, 129.6, 127.8, 127.7, 127.6, 127.5, 127.4, 121.9, 115.4, 115.1, 114.5, 114.2, 61.1, 33.1, 13.0 ; IR (neat) 3316, 2985, 1660, 1605, 1511, 1227, 1157, 1019, 822, 592 cm -1 ; HRMS m / z (M + ) calcd. for C 24 H 20 F 2 O 3 : 394.1381. Found: 394.1383.

7) Allyl 4-cinnamoyl-3-hydroxybiphenyl-2-carboxylate (9)

(132 mg, 1.0 mmol) and allyl 3-oxobutanoate (71 mg, 0.5 mmol) were reacted in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) %) Were synthesized.

1 H NMR (300 MHz, CDCl 3) δ 10.92 (1H, s), 7.37-7.14 (11H, m), 6.74 (1H, d, J = 7.8 Hz), 6.52-6.38 (2H, m), 5.39- D, J = 17.1 Hz), 4.41 (2H, d, J = 5.4 Hz), 3.60 (2H, d, J = 6); 13 C NMR (75 MHz, CDCl 3) δ 171.0, 159.2, 142.9, 137.5, 133.8, 131.3, 130.7, 128.4, 128.2, 128.1, 127.9, 127.7, 127.6, 127.0, 126.6, 126.1, 122.0, 118.3, 111.7, 65.8 , 33.1; IR (neat) 3415, 3056, 1660, 1416, 1271, 1147, 975, 756 cm < -1 & gt ;; HRMS m / z (M +) calcd for C 25 H 22 O 3: 370.1569. Found: 370.1570.

8) (E) -Allyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl-

Cs 2 CO 3 (163 mg, 0.5 mmol) (E) -3- ( 4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and allyl 3-oxo-butanoate (71 mg, 0.5 mmol) in the presence To obtain a yellow liquid compound 10 (160 mg, 79%).

1 H NMR (300 MHz, CDCl 3) δ 11.01 (1H, s), 7.34-7.29 (3H, m), 7.19-7.14 (2H, m), 7.04-6.93 (4H, m), 6.71 (1H, d J = 7.5 Hz), 6.45 (1H, d, J = 15.9Hz), 6.37-6.27 (1H, m), 5.48-5.34 1H, d, J = 17.1Hz), 4.44 (2H, d, J = 5.7Hz), 3.58 (2H, d, J = 6.6Hz); 13 C NMR (75 MHz, CDCl 3) δ 170.8, 159.4, 141.9, 138.9, 133.8, 130.5, 130.0, 129.7, 129.6, 127.8, 127.5, 127.4, 122.1, 118.7, 115.4, 115.1, 114.6, 114.3, 111.7, 65.9 , 33.1; IR (neat) 3532, 3039, 2926, 1660, 1511, 1420, 1226, 975, 820, 513 cm -1 ; HRMS m / z (M +) calcd for C 25 H 20 F 2 O 3: 406.1381 Found: 406.1378.

9) (E) -Benzyl 3-hydroxy-2'-methoxy-4- (3- (2- methoxyphenyl) allyl)

(162 mg, 1.0 mmol) and benzyl 3-oxobutanoate (86 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) Was reacted to synthesize a yellow liquid compound 11 (180 mg, 74%).

1 H NMR (300 MHz, CDCl 3) δ 11.02 (1H, s), 7.46 (1H, d, J = 8.1 Hz), 7.37 (1H, d, J = 7.5 Hz), 7.22-7.16 (6H, m) , 6.98-6.81 (6H, m), 6.69 (1H, d, J = 7.5 Hz), 6.63 (1H, d, J = 8.1 Hz), 6.49-6.39 3.84 (3H, s), 3.64 (2H, d, J = 3.9 Hz), 3.50 (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 171.1, 158.6, 156.3, 155.9, 138.3, 134.5, 133.9, 131.9, 129.3, 128.6, 128.3, 128.2, 128.1, 128.0, 127.99, 127.95, 126.6, 126.5, 125.9, 122.3 , 120.5, 120.3, 112.7, 110.7, 109.9, 66.7, 55.4, 55.0, 33.5; IR (neat) 3480, 3013, 2950, 1680, 1519, 1450, 1221, 980, 840, 507 cm -1 ; HRMS m / z (M + ) calcd for C 31 H 28 O 5 : 480.1937. Found: 480.1937.

10) 4-cinnamylmethyl-3-hydroxy-N-phenylbiphenyl-2-carboxamide (12)

Cs 2 CO 3 (163 mg, 0.5 mmol) under the presence Shinan aldehyde (132 mg, 1.0 mmol) and 3-oxo-phenylbutane -N- amide by reacting (89 mg, 0.5 mmol) of solid compound 12 (170 mg, 84%).

mp 128-130 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 12.03 (1H, s), 7.45-7.36 (5H, m), 7.32-7.26 (2H, m), 7.23-7.18 (3H, m), 7.15-7.09 (3H m), 6.99-6.94 (2H, m), 6.85 (2H, d, J = 7.8 Hz), 6.69 d, J = 6.6 Hz); 13 C NMR (75 MHz, CDCl 3) δ 168.5, 159.3, 140.5, 138.9, 137.5, 136.4, 132.7, 131.2, 129.3, 129.2, 129.2, 128.8, 128.4, 127.9, 127.0, 126.1, 124.8, 121.4, 120.2, 120.1 , 114.3, 33.2; IR (KBr) 3396, 3027, 1631, 1536, 1418, 1239, 1034, 827, 602, 519 cm -1 ; HRMS m / z (M +) calcd for C 28 H 23 NO 2: 405.1729. Found: 405.1732.

11) (E) -4'-Fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy-

Cs 2 CO 3 (163 mg, 0.5 mmol) there under (E) -3- (4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and 3-oxo-phenylbutane -N- amide (89 mg, 0.5 mmol) were reacted to synthesize a solid compound 13 (171 mg, 78%).

mp 68-70 [deg.] C; 1 H NMR (300 MHz, CDCl 3 )? 11.92 (1H, s), 7.54-7.49 (2H, m), 7.43-7.38 (3H, m), 7.34-7.26 (4H, m), 7.18-7.13 m), 7.09-7.01 (5H, m), 6.83 (1H, d, J = 7.8 Hz), 6.56 (1H, d, J = 15.9 Hz), 6.49-6.39 d, J = 6.6 Hz); 13 C NMR (75 MHz, CDCl 3) δ 168.3, 159.2, 137.8, 136.3, 132.8, 131.0, 130.9, 130.1, 129.0, 128.9, 127.7, 127.6, 127.5, 127.4, 125.0, 121.6, 120.1, 116.5, 116.2, 115.4 , 115.1, 33.2; IR (KBr) 3401, 2923, 1680, 1600, 1511, 1440, 1229, 819, 597 cm -1 ; HRMS m / z (M +) calcd for C 28 H 21 F 2 NO 2: 441.1540. Found: 441.1542.

12) 4- cinnamyl-3-hydroxy-N- (4-methoxyphenyl) biphenyl-2-carboxamide (14)

Was reacted with cinnamaldehyde (132 mg, 1.0 mmol) and N- (4-methoxyphenyl) -3-oxobutanamide (104 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, Compound 14 (165 mg, 76%) was synthesized.

mp 125-127 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 12.01 (1H, s), 7.44-7.33 (5H, m), 7.29 (2H, d, J = 7.2 Hz), 7.23-7.16 (3H, m), 7.12- (1H, m), 7.06 (1H, m), 6.85 (1H, s), 6.76 (2H, d, J = 8.7Hz), 6.68-6.62 (3H, s), 3.54 (2H, d, J = 6.0 Hz); 13 C NMR (75 MHz, CDCl 3) δ 168.2, 159.2, 156.7, 140.5, 138.9, 137.5, 132.5, 131.2, 129.5, 129.2, 128.7, 128.4, 128.3, 128.0, 126.9, 126.0, 122.0, 121.9, 121.3, 114.4 , 113.9, 55.3, 33.1; IR (KBr) 3404, 2929, 1603, 1512, 1420, 1231, 825, 594, 517 cm -1 ; HRMS m / z (M + ) calcd for C 29 H 25 NO 3 : 435.1834. Found: 435.1832.

13) Synthesis of (E) -3-hydroxy-4'-methoxy-N- (4-methoxyphenyl) -4- (3- (4- methoxyphenyl) allyl) biphenyl- 15)

Under Cs 2 CO 3 (163 mg, 0.5 mmol) exist (E) -3- (4- methoxyphenyl) acrylic aldehyde (162 mg, 1.0 mmol) and N- (4- methoxy-phenyl) -3-oxo-butane Amide (104 mg, 0.5 mmol) was reacted to synthesize a solid compound 15 (180 mg, 73%).

mp 62-64 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 12.08 (1H, s), 7.37-7.27 (5H, m), 7.08 (1H, s), 7.00 (2H, d, J = 9.0 Hz), 6.93-6.89 ( (1H, m), 6.83-6.71 (5H, m), 6.45 (1H, d, J = 15.9Hz), 6.34-6.24 (3H, s), 3.58 ( 2H, d, J = 6.6 Hz; 13 C NMR (75 MHz, CDCl 3) δ 168.5, 159.8, 159.2, 158.7, 156.8, 138.5, 132.6, 132.5, 130.6, 130.5, 129.6, IR (KBr) 3413, 3056, 1663, 1610, 1391, 1264, 1129, 748, 592 cm, 128.6, 127.2, 125.9, 122.1, 122.0, 121.5, 114.6, 114.4, 114.0, 113.8, 55.5, -1 ; HRMS m / z (M + ) calcd for C 31 H 29 NO 5 : 495.2046. Found: 495.2043.

14) Synthesis of (E) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy-N- (4-methoxyphenyl) biphenyl- 16)

Cs 2 CO 3 under (163 mg, 0.5 mmol) exist (E) -3- (4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and N- (4-methoxy-phenyl) -3-oxo-butane Amide (104 mg, 0.5 mmol) was reacted to synthesize Compound (16) (190 mg, 81%) as a solid.

mp 117-119 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 11.84 (1H, s), 7.45-7.38 (2H, m), 7.34-7.29 (3H, m), 7.20-7.15 (2H, m), 6.99-6.88 (5H (1H, m), 6.78-6.73 (3H, m), 6.47 (1H, d, J = 15.9 Hz), 6.40-6.30 Hz); 13 C NMR (75 MHz, CDCl 3) δ 168.1, 159.0, 156.9, 137.7, 132.6, 131.0, 130.9, 130.0, 129.4, 128.8, 127.7, 127.6, 127.4, 121.9, 121.5, 116.4, 116.1, 115.4, 115.1, 114.7 , 114.1, 55.4, 33.2; IR (KBr) 3404, 2929, 1603, 1512, 1420, 1231, 825, 517 cm -1 ; HRMS m / z (M + ) calcd for C 29 H 23 F 2 NO 3 : 471.1646. Found: 471.1645.

Synthesis of 4-cinnamoyl-3-hydroxy-N-p-tolylbiphenyl-2-carboxamide (17)

(132 mg, 1.0 mmol) and 3-oxo-N -tolylbutanamide (95 mg, 0.5 mmol) were reacted in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) 77%).

mp 98-100 C; 1 H NMR (300 MHz, CDCl 3) δ 12.03 (1H, s), 7.45-7.36 (5H, m), 7.29 (2H, d, J = 7.5 Hz), 7.21-7.16 (3H, m), 7.12- (2H, m), 3.55 (2H, d, J = 6.6Hz), 2.15 (2H, (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 168.3, 159.3, 140.5, 138.9, 137.5, 134.5, 133.9, 132.6, 131.2, 129.3, 129.2, 129.1, 128.7, 128.6, 128.4, 128.0, 126.9, 126.1, 121.3, 120.2 , 114.4, 33.1, 20.8; IR (KBr) 3394, 3028, 2921, 1635, 1532, 1417, 1237, 816, 760, 507 cm -1 ; HRMS m / z (M + ) calcd for C 29 H 25 NO 2 : 419.1885. Found: 419.1888.

16) (E) -3-Hydroxy-4'-methoxy-4- (3- (4- methoxyphenyl) allyl) -N-

Cs 2 CO 3 (163 mg, 0.5 mmol) in the presence (E) -3- (4- methoxyphenyl) acrylic aldehyde (162 mg, 1.0 mmol) and 3-oxo-tolyl -Np- butane amide (95 mg, 0.5 mmol) were reacted to prepare a solid compound 18 (182 mg, 76%).

mp 58-60 [deg.] C; 1 H NMR (300 MHz, CDCl 3) 12.08 (1H, s), 7.37-7.27 (5H, m), 7.13 (1H, s), 7.03-6.98 (4H, m), 6.87 (2H, d, J = (1H, d, J = 8.9 Hz), 6.81 (2H, d, J = 8.7 Hz), 6.73 (3H, s), 3.77 (3H, s), 3.59 (2H, d, J = 6.9 Hz), 2.25 (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 168.6, 159.8, 159.3, 158.7, 138.6, 134.6, 134.0, 132.6, 132.5, 130.6, 130.5, 130.4, 129.3, 128.7, 127.2, 125.9, 121.6, 120.3, 114.7, 114.4 , 113.8, 55.4, 55.2, 33.1, 20.8; IR (KBr) 3409, 2933, 1675, 1612, 1510, 1274, 1129, 1029, 834, 736, 506 cm -1 ; HRMS m / z (M + ) Calcd for C 31 H 29 NO 4 : 479.2097. Found: 479.2095.

17) (E) -4'-Fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy-

Cs 2 CO 3 (163 mg, 0.5 mmol) there under (E) -3- (4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and 3-oxo-tolyl -Np- butane amide (95 mg, 0.5 mmol) were reacted to synthesize a solid compound 19 (182 mg, 80%).

mp 104-106 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 11.84 (1H, s), 7.45-7.40 (2H, m), 7.34-7.29 (3H, m), 7.20-7.14 (2H, m), 7.04-7.86 (7H (1H, m), 6.74 (1H, d, J = 7.8 Hz), 6.47 (1H, d, J = 15.9 Hz), 6.40-6.30 (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 168.2, 159.1, 137.7, 134.9, 133.8, 132.7, 131.0, 130.9, 130.0, 129.5, 128.8, 127.7, 127.6, 127.5, 127.4, 121.6, 120.2, 116.4, 116.1, 115.4 , 115.1, 33.2, 20.8; IR (KBr) 3404, 2923, 1636, 1601, 1513, 1421, 1229, 1158, 817, 509 cm -1 ; HRMS m / z (M + ) calcd for C 29 H 23 F 2 NO 2 : 455.1697. Found: 455.1698.

18) 4- cinnamoyl-3-hydroxy-N-o-tolylbiphenyl-2-carboxamide (20)

(132 mg, 1.0 mmol) and 3-oxo-N-tolyl butanamide (95 mg, 0.5 mmol) were reacted in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) , 74%).

1 H NMR (600 MHz, CDCl 3) δ 11.90 (1H, s), 7.70 (1H, d, J = 8.4 Hz), 7.48 (2H, d, J = 7.2 Hz), 7.43 (2H, t, J = 7.8 Hz), 7.38-7.37 (3H, m), 7.33 (IH, d, J = 7.8 Hz), 7.28 (1H, m), 7.13 (1H, m), 7.03-6.99 (3H, m), 6.76 (1H, d, J = 7.2Hz) 3.63 (2H, d, J = 6.6 Hz), 1.62 (3H, s); 13 C NMR (150 MHz, CDCl 3) δ 168.9, 159.1, 140.5, 138.9, 137.5, 134.8, 132.6, 131.3, 130.4, 129.5, 129.3, 129.2, 128.7, 128.5, 128.4, 128.0, 127.0, 126.5, 126.1, 125.5 , 122.7, 121.9, 114.7, 33.2, 17.0; IR (neat) 3407, 3027, 1634, 1530, 1452, 1238, 754, 599, 517 cm -1 ; HRMS m / z (M + ) calcd for C 29 H 25 NO 2 : 419.1885. Found: 419.1888.

19) (E) -4'-Fluoro-4- (3- (4- fluorophenyl) allyl) -3-hydroxy-

Cs 2 CO 3 (163 mg, 0.5 mmol) there under (E) -3- (4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and 3-oxo-tolyl -No- butane amide (95 mg, 0.5 mmol) were reacted to synthesize a yellow liquid compound 21 (177 mg, 78%).

1 H NMR (300 MHz, CDCl 3) δ 11.72 (1H, s), 7.71 (1H, d, J = 8.7 Hz), 7.48-7.44 (2H, m), 7.35-7.30 (2H, m), 7.19- (2H, m), 6.99-6.93 (3H, m), 6.73 (1H, d, J = 8.7 Hz), 6.48 6.30 (1H, m), 3.61 (2H, d, J = 6.6 Hz), 1.68 (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 168.7, 159.0, 137.7, 136.5, 137.6, 132.7, 131.0, 130.9, 130.5, 130.1, 128.8, 127.7, 127.6, 127.6, 127.5, 126.7, 125.7, 122.6, 122.0, 116.4 , 116.1, 115.4, 115.1, 33.2, 17.0; IR (neat) 3414, 2926, 1636, 1513, 1229, 1157, 820, 755, 513 cm < -1 & gt ;; HRMS m / z (M + ) calcd for C 29 H 23 F 2 NO 2 : 455.1697. Found: 455.1698.

20) N- (4-chlorophenyl) -4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxamide (22)

(132 mg, 1.0 mmol) was reacted with N- (4-chlorophenyl) -3-oxobutanamide (106 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) 22 (168 mg, 76%).

mp 80-82 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 11.92 (1H, s), 7.48-7.38 (5H, m), 7.35-7.30 (2H, m), 7.28-7.21 (3H, m), 7.19-7.09 (3H (2H, m), 6.99 (1H, s), 6.82 (2H, d, J = 8.7 Hz), 6.73 (1H, d, J = 8.7 Hz), 6.52-6.36 ); 13 C NMR (75 MHz, CDCl 3) δ 168.5, 159.4, 140.4, 138.9, 137.5, 135.0, 132.9, 131.3, 129.8, 129.3, 129.2, 128.9, 128.8, 128.5, 128.4, 127.9, 127.0, 126.1, 121.5, 121.2 , 114.1, 33.1; IR (KBr) 3390, 3057, 1636, 1532, 1413, 1236, 1096, 750, 506 cm -1 ; HRMS m / z (M +) calcd for C 28 H 22 ClNO 2: 439.1339. Found: 439.1335.

21) (E) -N- (4-Chlorophenyl) -3-hydroxy-4'-methoxy-4- (3- (4- methoxyphenyl) allyl) biphenyl- )

Under Cs 2 CO 3 (163 mg, 0.5 mmol) exist (E) -3- (4- methoxyphenyl) acrylic aldehyde (162 mg, 1.0 mmol) and N- (4- chloro-phenyl) -3-oxo-butane amide (106 mg, 0.5 mmol) were reacted to synthesize a solid compound 23 (195 mg, 78%).

mp 130-132 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 11.94 (1H, s), 7.36-7.29 (5H, m), 7.16 (3H, d, J = 8.4 Hz), 7.00 (2H, d, J = 8.4 Hz) , 6.93 (1H, d, J = 8.4 Hz), 6.81 (2H, d, J = 8.4 Hz) (1H, m), 3.85 (3H, s), 3.77 (3H, s), 3.59 (2H, d, J = 6.6 Hz); 13 C NMR (75 MHz, CDCl 3) δ 168.8, 159.9, 159.4, 158.8, 138.6, 135.2, 132.9, 132.5, 130.7, 130.5, 130.4, 129.8, 128.9, 128.9, 127.2, 125.8, 121.7, 121.3, 114.7, 114.1 , 113.9, 55.5, 55.2, 33.1; IR (KBr) 3409, 2930, 1639, 1511, 1278, 1128, 817, 557 cm- 1 ; HRMS m / z (M + ) calcd for C 30 H 26 ClNO 4 : 499.1550. Found: 499.1550.

22) (E) -N- (4-Chlorophenyl) -4'-fluoro-4- (3- (4- fluorophenyl) allyl) -3-hydroxybiphenyl-2-carboxamide )

Cs 2 CO 3 (E) -3- ( 4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and N- (4-chlorophenyl) under (163 mg, 0.5 mmol) there-3-oxo-butane amide (106 mg, 0.5 mmol) were reacted to synthesize a solid compound 24 (185 mg, 78%).

mp 127-129 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 11.72 (1H, s), 7.44-7.40 (2H, m), 7.34-7.30 (3H, m), 7.21-7.17 (4H, m), 6.99-6.93 (5H (1H, m), 6.75 (1H, d, J = 7.8Hz), 6.47 (1H, d, J = 15.9Hz). 6.39-6.39 (1H, m), 3.60 (2H, d, J = 6.6Hz); 13 C NMR (75 MHz, CDCl 3) δ 168.3, 159.2, 137.7, 136.3, 136.2, 134.9, 133.6, 133.0, 131.0, 130.9, 130.1, 129.0, 127.5, 127.4, 121.7, 121.2, 116.5, 116.2, 115.4, 115.1 , 114.4, 33.1; IR (KBr) 3400, 2923, 1688, 1513, 1229, 1095, 823, 508 cm -1 ; HRMS m / z (M +) calcd for C 28 H 20 ClF 2 NO 3: 475.1151. Found: 475.1150.

23) (E) -N- (4-Chlorophenyl) -3-hydroxy-2'-methoxy- 4- (3- (2- methoxyphenyl) allyl) biphenyl- )

(162 mg, 1.0 mmol) and N- (4-chlorophenyl) -3-oxobutanamide in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) (106 mg, 0.5 mmol) were reacted to synthesize yellow liquid compound 25 (187 mg, 75%).

1 H NMR (600 MHz, CDCl 3) δ 11.90 (1H, s), 7.60-7.55 (3H, m), 7.54-7.49 (2H, m), 7.31-7.25 (4H, m), 7.07-6.96 (6H (1H, m), 6.83 (1H, d, J = 7.2 Hz), 6.60-6.55 (1H, m), 3.96 ; 13 C NMR (150 MHz, CDCl 3) δ 168.8, 158.5, 156.5, 156.3, 135.4, 134.5, 133.0, 130.6, 130.3, 129.8, 129.5, 129.2, 129.1, 128.8, 128.6, 128.0, 126.6, 126.0, 121.8, 121.6 , 121.0, 120.5, 115.2, 111.2, 110.8, 55.6, 55.4, 33.6; IR (neat) 3430, 2941, 1680, 1525, 1235, 1080, 807, 509 cm < -1 & gt ;; HRMS m / z (M + ) calcd for C 30 H 26 ClNO 4 : 499.1550. Found: 499.1550.

24) N- (2-Chlorophenyl) -4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxamide (26)

Was reacted with cinnamaldehyde (132 mg, 1.0 mmol) and N- (2-chlorophenyl) -3-oxobutanamide (106 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) Compound 26 (162 mg, 74%) was synthesized.

1 H NMR (300 MHz, CDCl 3) δ 11.43 (1H, s), 8.30 (1H, d, J = 8.1 Hz Hz), 7.55 (1H, s), 7.38-7.06 (13H, m), 6.88 (1H , t, J = 7.5 Hz), 6.71 (1H, d, J = 7.8 Hz), 6.48-6.34 (2H, m), 3.55 (2H, d, J = 6.6 Hz); 13 C NMR (75 MHz, CDCl 3) δ 169.0, 158.8, 139.8, 139.2, 137.5, 133.8, 133.0, 131.3, 129.4, 129.3, 129.1, 129.0, 128.6, 128.5, 128.4, 127.9, 127.4, 127.0, 126.1, 125.0 , 122.1, 121.6, 114.9, 33.2; IR (neat) 3376, 3028, 2924, 1639, 1589, 1528, 1437, 1297, 1234, 966, 753, 609 cm -1 ; HRMS m / z (M +) calcd for C 28 H 22 ClNO 2: 439.1339. Found: 439.1340.

25) (E) -N- (2-Chlorophenyl) -3-hydroxy-4'-methoxy-4- (3- (4- methoxyphenyl) allyl) biphenyl- )

(162 mg, 1.0 mmol) and N- (2-chlorophenyl) -3-oxobutanamide in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) (106 mg, 0.5 mmol) were reacted to synthesize a yellow liquid compound 27 (177 mg, 71%).

1 H NMR (600 MHz, CDCl 3) δ 11.54 (1H, s), 8.40 (1H, d, J = 8.4 Hz), 7.77 (1H, s), 7.37 (2H, d, J = 8.4 Hz), 7.30 (2H, m), 6.76-6. 16 (2H, m), 6.76 (1H, m) (1H, d, J = 7.2 Hz), 6.45 (1H, d, J = 15.0 Hz) 6.32-6.27 (1H, m), 3.79 (3H, s) = 6.0 Hz); 13C NMR (150 MHz, CDCl 3 ) δ 169.2, 160.1, 158.9, 158.7, 138.8, 133.9, 132.9, 132.1, 130.7, 130.6, 130.4, 129.0, 128.4, 127.4, 127.2, 125.8, 124.9, 123.0, 122.1, 121.6, 114.8, 114.6, 113.8, 55.4, 55.2, 33.1; IR (neat) 3415, 2950, 1609, 1530, 1422, 1230, 822, 594, 519 cm -1 ; HRMS m / z (M + ) calcd for C 30 H 26 ClNO 4 : 499.150. Found: 499.

26) (E) -N- (2-Chlorophenyl) -4'-fluoro-4- (3- (4- fluorophenyl) allyl) -3-hydroxybiphenyl- )

Cs 2 CO 3 (E) -3- ( 4-fluorophenyl) acrylic aldehyde (150 mg, 1.0 mmol) and N- (2- chlorophenyl) under (163 mg, 0.5 mmol) there-3-oxo-butane amide (106 mg, 0.5 mmol) were reacted to synthesize yellow liquid compound 28 (189 mg, 76%).

1 H NMR (300 MHz, CDCl 3 )? 11.34 (1H, s), 8.39 (1H, d, J = 8.1 Hz), 7.59 (1H, s), 7.42-7.38 (1H, m), 7.21-7.16 (2H, m), 7.06 (2H, t, J = 7.8 Hz), 6.99-6.90 (3H, m), 6.75 , J = 15.9Hz), 6.37-6.27 (1H, m), 3.58 (2H, d, J = 6.6Hz); 13 C NMR (75 MHz, CDCl 3) δ 168.7, 158.7, 138.0, 135.8, 133.7, 133.6, 133.0, 131.1, 131.0, 130.1, 129.1, 128.6, 127.6, 127.5, 127.4, 125.1, 122.8, 122.2, 121.4, 116.3 , 116.0, 115.4, 115.1, 33.2; IR (neat) 3380, 2924, 1640, 1594, 1524, 1435, 1228, 1157, 819, 754, 606, 516 cm -1 ; HRMS m / z (M +) calcd for C 28 H 20 ClF 2 NO 2: 475.1151. Found: 475.1152.

27) 1- (4-cinnamyl-3-hydroxy- [1,1'-biphenyl] -2-yl) ethan-

Cs 2 CO 3 (163 mg, 0.5 mmol) under the presence Shinan aldehyde (132 mg, 1.0 mmol) and pentane-2,4-dione (50 mg, 0.5 mmol) to a compound of a yellow liquid 29 (78 mg, 48 reaction %) Were synthesized.

1 H NMR (600 MHz, CDCl 3) δ 11.93 (1H, s), 7.41-7.26 (10H, m), 7.19-7.15 (1H, m), 6.78 (1H, d, J = 7.8 Hz), 6.50 ( 1H, d, J = 15.6Hz), 6.44-6.39 (1H, m), 3.59 (2H, d, J = 6.6Hz), 1.84 (3H, s); 13 C NMR (150 MHz, CDCl 3 )? 207.4, 158.9, 142.8, 134.0, 131.3, 129.0, 128.9, 128.6, 128.4, 128.0, 127.9, 127.4, 127.0, 126.1, 121.6, 120.8, 118.7, 33.0, 31.7; IR (neat) 3380, 3042, 1720, 1426, 1266, 760, 508 cm -1 ; HRMS m / z (M + ) calcd for C 23 H 20 O 2 : 328.1463. Found: 328.1462.

Example 2 Synthesis of cinnamaldehyde-3-d (2e)

(Triphenylphosphoranylidene) acetaldehyde (1 gm, 3.3 mmol) and benzaldehyde-alpha-d 1 (321 mg, 3.3 mmol) were added to a two necked round bottom flask blocked with nitrogen using toluene (8.0 mL) 3.0 mmol) was heated at 70 < 0 > C for 16 h. After completion of the reaction, the reaction was confirmed by TLC. Thereafter, the reaction solvent was evaporated under reduced pressure in a rotary evaporator to obtain a residue. The residue was purified by flash column chromatography on silica gel to obtain the desired compound.

1) Synnamic aldehyde-3-d (2e)

Colorless liquid, yield: 53%

1 H NMR (600 MHz, CDCl 3) δ 9.68 (1H, d, J = 7.8 Hz), 7.54-7.53 (2H, m), 7.41-7.40 (3H, m), 6.68 (1H, d, J = 8.4 Hz; 13 C NMR (150 MHz , CDCl 3) δ 193.5, 152.4, 152.1, 133.8, 131.1, 129.0, 128.4; IR (neat) 3045, 2825, 2740, 1685, 1492, 971, 605 cm -1; HRMS m / z (M < + & gt ; ) calcd for C 9 H 7 DO: 133.0638. Found: 133.0636.

2) (E) -3- hydroxy -N- (4- methoxyphenyl) -4- (3-phenyl-allyl -1,3-d 2) - [1,1'- biphenyl] -2-carboxylic (34)

Under refluxing toluene Cs 2 CO 3 (163 mg, 0.5 mmol) in the presence Shinan aldehyde -3-d (133 mg, 1.0 mmol) and (4-methoxyphenyl) butane-3-oxo-amide (104 mg, 0.5 mmol) To obtain a solid compound 34 (155 mg, 71%).

mp 126-128 [deg.] C; 1 H NMR (600 MHz, CDCl 3) δ 12.08 (1H, s), 7.50-7.44 (5H, m), 7.38 (2H, d, J = 7.8 Hz), 7.32 (1H, d, J = 7.2 Hz) , 7.28 (2H, t, J = 7.8 Hz), 7.18 (1H, t, J = 7.8 Hz), 6.94 m), 6.45 (1H, d, J = 6.6Hz), 3.73 (3H, s), 3.62 (1H, m); 13 C NMR (75 MHz, CDCl 3) δ 168.2, 159.2, 156.8, 140.6, 138.9, 137.5, 132.6, 129.5, 129.2, 128.7, 128.5, 128.44, 128.41, 127.9, 127.0, 126.1, 126.0, 122.0, 121.3, 114.4 , 114.0, 55.4, 33.1; IR (KBr) 3404, 2929, 1603, 1512, 1420, 1231, 825, 594, 517 cm -1 ; HRMS m / z (M + ) calcd for C 29 H 23 D 2 NO 3 : 437.1960. Found: 437.1963.

Example 3 Synthesis of 4-benzyl-3-hydroxy-N-phenylbiphenyl-2-carboxamide and alkyl 4-benzyl-3-hydroxybiphenyl-2-carboxylate derivative (36-39)

To a solution of (E) -3- (4-methoxyphenyl) acrylaldehyde (0.5 mmol), aryl-aldehyde 35a-35b (1.0 mmol) and a ketone ester or ketone amide (1a, 1b, ) (0.5 mmol) in DMF (5 mL) was added Cs 2 CO 3 (0.5 mmol). Each reaction mixture was refluxed for 5-6 hours. Thereafter, the reaction solvent was evaporated under reduced pressure in a rotary evaporator to obtain a residue. The residue was purified by flash column chromatography on silica gel to obtain the desired compound.

1) Methyl 4- (2-chlorobenzyl) -3-hydroxy-4'-methoxybiphenyl-2-carboxylate (36)

Cs 2 CO 3 (163 mg, 0.5 mmol) in the presence (E) -3- (4- methoxyphenyl) acrylic aldehyde (81 mg, 0.5 mmol), 2- chloro-benzaldehyde (140 mg, 1.0 mmol) and methyl 3 -Oxobutanoate (58 mg, 0.5 mmol) were reacted to synthesize yellow liquid compound 36 (126 mg, 66%).

1 H NMR (600 MHz, CDCl 3) δ 10.79 (1H, s), 7.31 (1H, d, J = 6.6 Hz), 7.17-7.16 (1H, m), 7.13-7.10 (2H, m), 7.07- (2H, s), 3.76 (3H, s), 3.44 (3H, m), 6.81 (2H, d, J = 8.4 Hz), 6.64 ); 13 C NMR (150 MHz, CDCl 3 ) δ 171.8, 159.1, 158.6, 142.6, 137.6, 135.2, 134.4, 134.0, 131.1, 129.4, 129.2, 127.6, 126.7, 126.5, 122.1, 113.0, 111.8, ; IR (neat) 3450, 2960, 1663, 1594, 1523, 1435, 1225, 1147, 827, 754, 606, 552 cm -1 ; HRMS m / z (M +) calcd for C 22 H 19 ClO 4: 382.0972. Found: 382.0969.

2) Ethyl 4- (2-bromobenzyl) -3-hydroxy-4'-methoxybiphenyl-

Under Cs 2 CO 3 (163 mg, 0.5 mmol) exist (E) -3- (4- methoxyphenyl) acrylic aldehyde (81 mg, 0.5 mmol), 2- bromo-benzaldehyde (184 mg, 1.0 mmol) and ethyl 3-oxobutanoate (65 mg, 0.5 mmol) was reacted to synthesize a yellow liquid compound 37 (143 mg, 68%).

1 H NMR (600 MHz, CDCl 3) δ 11.03 (1H, s), 7.57 (1H, d, J = 7.2 Hz), 7.27-7.22 (2H, m), 7.22-7.19 (2H, m), 7.12 ( (2H, d, J = 8.7 Hz), 7.08 (2H, d, J = 7.2 Hz), 6.86 Hz), 3.82 (3H, s), 0.81 (3H, t, J = 7.2 Hz); 13 C NMR (150 MHz, CDCl 3) δ 171.4, 159.3, 158.6, 142.8, 139.4, 135.5, 133.8, 132.7, 131.1, 129.3, 127.8, 127.4, 126.5, 125.0, 122.0, 113.0, 112.0, 61.0, 55.3, 35.6 , 13.2; IR (neat) 3371, 2932, 1675, 1530, 1435, 1251, 1138, 737, 521 cm < -1 & gt ;; HRMS m / z (M +) calcd for C 23 H 21 BrO 4: 440.0623. Found: 440.0622.

3) Preparation of 4- (2-chlorobenzyl) -3-hydroxy-4'-methoxy-N-

Cs 2 CO 3 under (163 mg, 0.5 mmol) exist (E) -3- (4- methoxyphenyl) acrylic aldehyde (81 mg, 0.5 mmol), 2- chloro-benzaldehyde (140 mg, 1.0 mmol) and 3- (95 mg, 0.5 mmol) was reacted to synthesize a yellow liquid compound 38 (155 mg, 65%).

1 H NMR (600 MHz, CDCl 3 )? 12.17 (1H, s), 7.39-7.35 (3H, m), 7.29-7.27 (1H, m), 7.20-7.14 (1H, d, J = 7.8 Hz), 7.02-6.98 (4H, m), 6.87 , < / RTI > s), 2.25 (3H, s); 13 C NMR (150 MHz, CDCl 3 )? 168.5, 159.8, 159.5, 138.8, 137.7, 134.6, 134.4, 134.0, 132.8, 132.5, 131.3, 130.5, 129.4, 129.4, 129.3, 127.6, 126.8, 121.5, 120.3, 114.7 , 114.4, 55.4, 33.1, 20.8; IR (neat) 3390, 2937, 1642, 1586, 1524, 1425, 1222, 1139, 850, 751, 614 cm -1 ; HRMS m / z (M +) calcd for C 28 H 24 ClNO 3: 457.1445. Found: 457.1443.

4) 4- (2-Chlorobenzyl) -N- (4-chlorophenyl) -3-hydroxy-4'-methoxybiphenyl-

Cs 2 CO 3 (163 mg, 0.5 mmol) there under (E) -3- (4- methoxyphenyl) acrylic aldehyde (81 mg, 0.5 mmol), 2- chloro-benzaldehyde (140 mg, 1.0 mmol) and N- (150 mg, 63%) was synthesized by reacting (4-chlorophenyl) -3-oxobutanamide (106 mg, 0.5 mmol)

1 H NMR (600 MHz, CDCl 3) δ 12.02 (1H, s), 7.39-7.34 (3H, m), 7.28 (1H, d, J = 7.2 Hz), 7.20-7.16 (5H, m), 7.09 ( (1H, d, J = 7.8 Hz), 7.00 (2H, d, J = 8.7 Hz), 6.93 s), 3.85 (3H, s); 13 C NMR (150 MHz, CDCl 3) δ 168.7, 159.9, 159.6, 138.8, 137.6, 135.2, 134.4, 133.1, 132.3, 131.3, 130.5, 129.8, 129.4, 128.9, 127.8, 127.6, 126.8, 121.6, 121.3, 114.7 , 114.1, 55.5, 33.1; IR (neat) 3410, 2956, 1621, 1579, 1535, 1227, 1143, 749, 507 cm < -1 & gt ;; HRMS m / z (M + ) calcd for C 27 H 21 Cl 2 NO 3 : 477.0898. Found: 477.0897.

Example 4 Compound 40-45 Synthesis

Cs 2 CO 3 (0.5 mmol) was added to a solution of cinnamaldehyde (2e-2f) (1.0 mmol) and a ketone ester or ketoneamide (1a-1c or 1i) (0.5 mmol) dissolved in toluene . Each reaction mixture was refluxed for 4-8 hours. Thereafter, the reaction solvent was evaporated under reduced pressure in a rotary evaporator to obtain a residue. The residue was purified by flash column chromatography on silica gel to obtain the desired compound.

1) (E) -methyl 6- (furan-2-yl) -3- (3- (furan-

(122 mg, 1.0 mmol) and methyl 3-oxobutanoate (58 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) To obtain a yellow liquid compound 40 (123 mg, 76%).

1 H NMR (600 MHz, CDCl 3) δ 10.49 (1H, s), 7.43 (1H, s), 7.30-7.28 (2H, m), 6.92 (1H, d, J = 7.8 Hz), 6.44-6.23 ( (2H, m), 6.25 (1H, d, J = 16.2 Hz), 6.14 (1H, d, J = 3.0 Hz) , 3.70 (3H, s), 3.55 (2H, d, J = 6.6 Hz); 13 C NMR (75 MHz, CDCl 3 ) 隆 171.2,158.6,154.0,152.9,142.1,141.4,133.8,130.8,128.7,126.6 IRMS (neat) 3396, 2952, 1635, 1594, 1525, 1435, 1236, 1161, 829, 751, 512 cm -1 ; HRMS m / z (M +) calcd for C 19 H 16 O 5: 324.0998 Found:. 324.0999.

2) (E) -Ethyl 6- (furan-2-yl) -3- (3- (furan-

(122 mg, 1.0 mmol) and ethyl 3-oxobutanoate (65 mg, 0.5 mmol) in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) To obtain a yellow liquid compound 41 (125 mg, 74%).

1 H NMR (300 MHz, CDCl 3) δ 10.77 (1H, s), 7.43 (1H, s), 7.33-7.29 (2H, m), 6.90 (1H, d, J = 7.5 Hz), 6.44-6.28 ( (2H, d, J = 6.0 Hz), 1.06 (3H, t, J = 7.2 Hz), 4.17 Hz); 13 C NMR (75 MHz, CDCl 3 )? 170.7, 158.9, 154.2, 152.9, 141.9, 141.7, 141.4, 133.7, 130.8, 128.8, 126.6, 121.6, 119.9, 111.9, 111.0, 106.8, 106.6, 61.4, 32.8, 13.7 ; IR (neat) 3378, 2950, 1655, 1594, 1529, 1435, 1228, 1153, 819, 754, 519 cm- 1 ; HRMS m / z (M +) calcd for C 20 H 18 O 5: 338.1154. Found: 338.1153.

3) Synthesis of (E) -allyl 6- (furan-2-yl) -3- (3- (furan-

(122 mg, 1.0 mmol) and allyl 3-oxobutanoate (71 mg, 0.5 mmol) were reacted in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) Compound 42 (134 mg, 77%) was synthesized.

1 H NMR (300 MHz, CDCl 3) δ 10.59 (1H, s), 7.40 (1H, s), 7.32-7.29 (2H, m), 6.91 (1H, d, J = 7.8 Hz), 6.42-6.39 ( 2H, m), 6.32-6.22 (3H, m), 6.14 (1H, d, J = 2.7 Hz), 5.75-5.62 (1H, m), 5.17-5.12 J = 5.7 Hz), 3.55 (2H, d, J = 6.3 Hz); 13 C NMR (75 MHz, CDCl 3 )? 170.5, 158.8, 154.1, 152.9, 142.0, 141.4, 133.9, 131.2, 130.8, 128.8, 126.6, 121.5, 119.9, 118.7, 111.6, 111.1, 111.0, 107.0, 106.6, , 32.8; IR (neat) 3395, 2934, 1645, 1594, 1438, 1239, 1158, 813, 760, 609, 517 cm < -1 & gt ;; HRMS m / z (M +) calcd for C 21 H 18 O 5: 350.1154. Found: 350.1153.

4) Synthesis of (E) -N- (4-chlorophenyl) -6- (furan-2-yl) -3-

(122 mg, 1.0 mmol) and N- (4-chlorophenyl) -3-oxobutanamide in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) (106 mg, 0.5 mmol) were reacted to synthesize a white solid compound 43 (157 mg, 75%).

mp 85-87 [deg.] C; 1 H NMR (600 MHz, CDCl 3) δ 11.23 (1H, s), 7.50 (1H, s), 7.28-7.26 (2H, m), 7.21-7.19 (5H, m), 6.91 (1H, d, J J = 3.0 Hz), 3.57 (2H, d, J = 7.8 Hz), 6.57 (1H, d, J = 3.0 Hz), 6.2 (1H, brs), 6.34-6.24 , ≪ / RTI > J = 6.6 Hz); 13 C NMR (150 MHz, CDCl 3) δ 168.1, 158.6, 152.9, 152.0, 144.0, 141.4, 135.5, 133.0, 130.1, 130.0, 129.0, 127.3, 126.5, 121.7, 121.1, 120.0, 114.7, 111.7, 111.1, 109.8 , 106.7, 32.9; IR (KBr) 3390, 2930, 1640, 1575, 1440, 1227, 1120, 826, 754, 528 cm -1 ; HRMS m / z (M + ) calcd for C24H18ClNO4: 419.0924. Found: 419.0924.

5) Synthesis of (E) -methyl 6- (anthracen-9-yl) -3- (3-

(232 mg, 1.0 mmol) and methyl 3-oxobutanoate (58 mg, 0.5 mmol) were reacted in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) The solid compound 44 (168 mg, 62%) was synthesized.

mp 90-91 [deg.] C; 1 H NMR (600 MHz, CDCl 3) δ 11.70 (1H, s), 8.35 (1H, s), 8.33-8.29 (3H, m), 7.94-7.89 (4H, m), 7.60 (1H, d, J = 7.8 Hz), 7.50-7.21 (1H, m), 6.79 (1H, d, J = 7.8 Hz), 6.29-6.24 s); 13 C NMR (150 MHz, CDCl 3) δ 171.4, 160.7, 139.3, 137.5, 136.3, 134.6, 133.2, 131.4, 131.1, 129.7, 129.6, 128.5, 128.4, 128.2, 127.2, 126.3, 126.2, 126.0, 125.8, 125.7 , 125.2, 125.0, 124.9, 123.8, 113.4, 51.7, 34.0; IR (KBr) 3420, 2950, 1646, 1591, 1531, 1434, 1241, 823, 754 cm < -1 & gt ;; HRMS m / z (M + ) calcd for C 39 H 28 O 3 : 544.2038. Found: 544.2037.

6) (E) -Ethyl 6- (anthracen-9-yl) -3- (3-

(232 mg, 1.0 mmol) and ethyl 3-oxobutanoate (65 mg, 0.5 mmol) were reacted in the presence of Cs 2 CO 3 (163 mg, 0.5 mmol) The solid compound 45 (167 mg, 60%) was synthesized.

mp 92-94 [deg.] C; 1 H NMR (600 MHz, CDCl 3 )? 11.93 (1H, s), 8.44 (1H, s), 8.40-8.37 (3H, m), 8.01-7.98 = 7.8 Hz), 7.52 (2H, d, J = 7.8 Hz), 7.49-7.40 (6H, m), 7.33-7.28 (3H, m), 6.87 (1H, m), 4.04 (2H, d, J = 6.6 Hz) 3.45 (2H, q, J = 7.2 Hz), -0.20 (3H, t, J = 7.2 Hz); 13 C NMR (150 MHz, CDCl 3) δ 170.9, 160.9, 139.3, 136.3, 134.5, 131.4, 131.2, 129.8, 129.7, 128.5, 128.4, 128.1, 127.2, 126.4, 126.3, 126.2, 126.0, 125.6, 125.2, 125.1 , 125.0, 124.95, 124.92, 123.6, 113.4, 60.5, 34.0, 11.9; IR (KBr) 3385, 2935, 1650, 1590, 1520, 1435, 1228, 1147, 819, 744, 612, 507 cm -1 ; HRMS m / z (M + ) calcd for C 40 H 30 O 3 : 558.2195. Found: 558.2192.

Example 5 Synthesis for Hydrogenation (Compounds 46-47)

A solution of Compound 3 or 14 dissolved in 15 mL of anhydrous ethyl acetate was placed in a reaction vessel of an atmospheric pressure hydrogenation apparatus, and 0.1 g of palladium-charcoal (10%) was added. The air was replaced with hydrogen and the reaction mixture was shaken at room temperature for 8 hours. The progress of the reaction was monitored by TLC (petroleum ether / ethyl acetate, 4: 1). After completion of the reaction, the palladium-charcoal was filtered off and the ethyl acetate was removed under vacuum to obtain compounds 46 and 47 in a yield of 99%.

1) Methyl 3-hydroxy-4- (3-phenylpropyl) biphenyl-2-carboxylate (46)

Hydrogenation of methyl 4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate (103 mg, 0.3 mmol) gave the yellow liquid compound 46 (102 mg, 99%).

1 H NMR (600 MHz, CDCl 3) δ 10.79 (1H, s), 7.33 (2H, t, J = 7.8 Hz), 7.29-7.25 (4H, m), 7.20 (4H, t, J = 7.2 Hz) , 7.16 (1H, t, J = 7.2 Hz), 6.72 (1H, d, J = 7.2 Hz), 3.45 (3H, s), 2.74-2.69 (4H, m), 2.01-1.96 (2H, m); 13 C NMR (75 MHz, CDCl 3) δ 171.8, 159.6, 142.9, 142.4, 142.3, 133.7, 129.6, 128.4, 128.2, 128.1, 127.5, 126.5, 125.6, 121.8, 111.6, 51.5, 35.7, 30.8, 29.6; IR (neat) 3440, 3050, 1660, 1436, 1276, 971, 767, 508 cm -1 ; HRMS m / z (M + ) calcd for C 23 H 22 O 3 : 346.1569. Found: 346.1569.

2) 3-Hydroxy-N- (4-methoxyphenyl) -4- (3-phenylpropyl) biphenyl-

Hydrogenation of 4-cinnamoyl-3-hydroxy-N- (4-methoxyphenyl) biphenyl-2-carboxamide (130 mg, 0.3 mmol) ).

mp 142-144 [deg.] C; 1 H NMR (600 MHz, CDCl 3) δ 12.03 (1H, s), 7.55-7.49 (5H, m), 7.35-7.28 (5H, m), 7.23 (1H, t, J = 7.2 Hz), 6.98 ( (1H, s), 6.91 (2H, d, J = 9.0 Hz), 6.80-6.77 (3H, m), 3.78 (3H, s), 2.84-2.77 ; 13 C NMR (150 MHz, CDCl 3 )? 168.3, 159.4, 156.7, 142.4, 140.7, 138.5, 132.5, 130.6, 129.5, 129.26, 129.22, 128.4, 128.3, 128.2, 125.6, 121.9, 121.1, 114.3, , 35.7, 30.8, 29.6; IR (KBr) 3430, 2940, 1608, 1512, 1231, 820, 590, 510 cm < -1 & gt ;; HRMS m / z (M + ) calcd for C 29 H 27 NO 3 : 437.1991. Found: 437.1990.

Example 6 Synthesis of Chromene (Compound 48-49)

To the stirred solution of anhydrous benzene (4 mL) was added the compound 3 or 14 (0.3 mmol) prepared above and DDQ (7.0 mg, 10 mol%) under nitrogen atmosphere. The reaction mixture was then refluxed for 10-12 hours. After completion of the reaction, the solvent was partially removed under vacuum and the reaction mixture was purified by flash chromatography (hexane / EtOAc) to give chromen 48 and 49.

1) Methyl 2,7-diphenyl-2H-chromen-8-carboxylate (48)

(103 mg, 0.3 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (7.0 mg, 10 mol%) were reacted to obtain 48 (65 mg, 63%) of a yellow solid.

mp 82-84 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 7.45-7.42 (2H, m), 7.35-7.29 (8H, m), 7.07 (1H, d, J = 7.8 Hz), 6.88 (1H, d, J = 7.8 Hz), 6.54 (1H, d, J = 9.9 Hz), 6.01-6.02 (1H, m), 5.91 (1H, dd, J = 3.6, 9.9 Hz), 3.44 (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 167.9, 150.3, 140.9, 140.5, 140.0, 128.5, 128.3, 128.1, 128.0, 127.5, 127.4, 126.4, 125.3, 123.0, 122.2, 121.7, 120.5, 79.9, 51.9; IR (KBr) 2980, 1675, 1588, 1520, 1435, 1225, 1150, 827, 610, 560 cm -1 ; HRMS m / z (M + ) calcd for C 23 H 18 O 3 : 342.1256. Found: 342.1255.

2) N- (4-methoxyphenyl) -2,7-diphenyl-2H-chromen-8-carboxamide (49)

(130 mg, 0.3 mmol) was reacted with DDQ (7.0 mg, 10 mol%) to obtain a yellow solid Compound 49 (84 mg, 65%) was obtained.

mp 153-155 [deg.] C; 1 H NMR (300 MHz, CDCl 3) δ 7.47-7.45 (4H, m), 7.34-7.24 (6H, m), 7.10-7.03 (3H, m), 6.92 (2H, d, J = 8.7 Hz), 6.74 (2H, d, J = 8.7 Hz), 6.63 (1H, d, J = 8.7 Hz), 6.00-5.93 (2H, m), 3.73 (3H, s); 13 C NMR (75 MHz, CDCl 3) δ 164.8, 156.4, 149.8, 141.1, 140.0, 139.8, 130.6, 128.6, 128.4, 128.3, 128.2, 127.6, 127.3, 126.9, 124.9, 124.8, 123.6, 122.7, 122.0, 120.8 , 113.9, 76.6, 55.4; IR (KBr) 2960, 1660, 1580, 1523, 1438, 1220, 1140, 827, 754, 606, 550 cm < -1 & gt ;; HRMS m / z (M + ) calcd for C 29 H 23 NO 3 : 433.1678. Found: 433.1678.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (14)

A biaryl compound represented by the following formula (1):
[Chemical Formula 1]
Figure 112015088834720-pat00012

In Formula 1,
A is selected from phenyl, furan-2-yl or anthracen-9-yl,
R 1 is C1 to C4 alkyl, alkoxy C1 to C4, -OCH 2 CH = CH 2 , PhNH-, 4-MeOC 6 H 4 NH-, 4-MeC 6 H 4 NH-, 2-MeOC 6 H 4 NH-, 2-MeC 6 H 4 NH-, 4-ClC 6 H 4 NH- , and 2-ClC 6 is selected from the group consisting of H 4 NH-,
R 2 and R 3 are the same or different and are selected from the group consisting of hydrogen, C 1 to C 4 alkyl, C 1 to C 4 alkoxy and halogen,
R 4 is 4-Shinan wheat, 3- (4-methoxyphenyl) allyl-3- (4-fluorophenyl) allyl, 4- (3-phenyl-allyl -1,3-d 2), 2- chloro-benzyl , 2-bromobenzyl, 3- (furan-2-yl) allyl, 3- (anthracen-9-yl) allyl and 3-phenylpropyl. The method of claim 1, wherein the biaryl compound is selected from the group consisting of methyl 4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -methyl 3-hydroxy- (E) -methyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl (E) -ethyl 3-hydroxy-4'-methoxy-4- (3- (4-methoxy- 2-carboxylate, (E) -ethyl 4'-fluoro-4- (3- (4- fluorophenyl) allyl) -3-hydroxybiphenyl- Cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -allyl 4'-fluoro-4- (3- (4- fluorophenyl) (E) -benzyl 3-hydroxy-2'-methoxy-4- (3- (2- methoxyphenyl) allyl) biphenyl-2-carboxylate , 4-cinnamylmethyl-3-hydroxy-N- (E) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy-N-phenylbiphenyl-2-carboxamide (E) -3-hydroxy-4'-methoxy-N- (4-methoxyphenyl) 4- (3- (4-methoxyphenyl) allyl) biphenyl-2-carboxamide, (E) (4-methoxyphenyl) biphenyl-2-carboxamide, 4-cinnamoyl-3-hydroxy-Np-tolyl biphenyl- (E) -4 ' -fluoro-biphenyl-2-carboxamide, 3-hydroxy-N-tolylbiphenyl-2-carboxamide, 4- cinnamylmethyl-3-hydroxy-N-tolylbiphenyl- Carboxamide, (E) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy- (E) -N- (4-chlorophenyl) - (4-chlorophenyl) -4-cinnamylmethyl 3-hydroxybiphenyl-2-carboxamide, (E) -N- (4-chlorophenyl) -4'- (3-hydroxy-4'-methoxy- Fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl-2-carboxamide, (E) 2-carboxamide, N- (2-chlorophenyl) -4-cinnamylmethyl-3-hydroxybiphenyl-2 -Carboxamide, (E) -N- (2-chlorophenyl) -3-hydroxy-4'-methoxy-4- (3- (4- methoxyphenyl) allyl) Amide, (E) -N- (2- chlorophenyl) -4'-fluoro-4- (3- (4- fluorophenyl) allyl) -3-hydroxybiphenyl- Ethan-1-one, (E) -3-hydroxy-N- (4-methoxyphenyl) ) -4- (3-phenyl-allyl -1,3-d 2) - [1,1'- biphenyl] -2-carboxamide, amide, methyl 4- (2-chlorobenzyl) -3-hydroxy-4 4-methoxybiphenyl-2-carboxylate, 4- (2-chlorobenzyl) -3-hydroxy- ) - 3-hydroxy-4'-methoxy-Np-tolylbiphenyl-2-carboxamide, 4- (2- chlorobenzyl) 2-carboxamide, (E) -methyl 6- (furan-2-yl) -3- (3- (furan-2-yl) allyl) -2-hydroxybenzoate, E) -ethyl 6- (furan-2-yl) -3- (3- (furan-2-yl) allyl) -2- hydroxybenzoate, 3- (3-furan-2-yl) allyl) -2-hydroxybenzoate, (E) (E) -methyl 6- (anthracen-9-yl) -3- (3- (anthracene-9-yl) allyl) -2-hydroxybenzamide, Hydroxybenzoate, (E) -ethyl 6- (anthracen-9-yl) - Methyl-3-hydroxy-4- (3-phenylpropyl) biphenyl-2-carboxylate and 3-hydroxy- N- (4-methoxyphenyl) -4- (3-phenylpropyl) biphenyl-2-carboxamide. A process for producing a biaryl compound characterized by refluxing a compound represented by the formula (1) and a compound represented by the formula (2) in the presence of Cs 2 CO 3 as a catalyst and toluene as a solvent,
[Reaction Scheme 1]
Figure 112015088834720-pat00013

In the above Reaction Scheme 1,
R 1 is C1 to C4 alkyl, alkoxy C1 to C4, -OCH 2 CH = CH 2 , PhNH-, 4-MeOC 6 H 4 NH-, 4-MeC 6 H 4 NH-, 2-MeOC 6 H 4 NH-, 2-MeC 6 H 4 NH-, 4-ClC 6 H 4 NH- , and 2-ClC 6 is selected from the group consisting of H 4 NH-,
R 2 and R 3 are the same or different and are selected from the group consisting of hydrogen, C 1 to C 4 alkyl, C 1 to C 4 alkoxy and halogen. The method of claim 3, wherein the biaryl compound is selected from the group consisting of methyl 4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -methyl 3-hydroxy- (E) -methyl 4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxybiphenyl (E) -ethyl 3-hydroxy-4'-methoxy-4- (3- (4-methoxy- 2-carboxylate, (E) -ethyl 4'-fluoro-4- (3- (4- fluorophenyl) allyl) -3-hydroxybiphenyl- Cinnamylmethyl-3-hydroxybiphenyl-2-carboxylate, (E) -allyl 4'-fluoro-4- (3- (4- fluorophenyl) (E) -benzyl 3-hydroxy-2'-methoxy-4- (3- (2- methoxyphenyl) allyl) biphenyl-2-carboxylate , 4-cinnamylmethyl-3-hydroxy-N- (E) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy-N-phenylbiphenyl-2-carboxamide (E) -3-hydroxy-4'-methoxy-N- (4-methoxyphenyl) 4- (3- (4-methoxyphenyl) allyl) biphenyl-2-carboxamide, (E) (4-methoxyphenyl) biphenyl-2-carboxamide, 4-cinnamylmethyl-3-hydroxy-Np-tolyl biphenyl- (E) -4 ' -fluoro-biphenyl-2-carboxamide, 3-hydroxy-N-tolylbiphenyl-2-carboxamide, 4- cinnamylmethyl-3-hydroxy-N-tolylbiphenyl- Carboxamide, (E) -4'-fluoro-4- (3- (4-fluorophenyl) allyl) -3-hydroxy-N (E) -N- (4-chlorophenyl) -4-cinnamylmethyl-3-hydroxybiphenyl-2-carboxamide, N- (E) -N- (4-chlorophenyl) - phenyl) -3-hydroxy-4'-methoxy- (E) -N- (4-chlorophenyl) -3-hydroxy-4-fluoro-4- 2-methoxy-4- (3- (2-methoxyphenyl) allyl) biphenyl-2-carboxamide, N- (2- chlorophenyl) -4- 2-carboxamide, (E) -N- (2-chlorophenyl) -3-hydroxy-4'-methoxy- 4- (3- (4- methoxyphenyl) -Carboxamide, (E) -N- (2-chlorophenyl) -4'-fluoro-4- (3- (4- fluorophenyl) allyl) -3-hydroxybiphenyl- Amide and 1- (4-cinnamyl-3-hydroxy- [1,1'-biphenyl] -2-yl) ethan- Process for producing a biaryl compound. A process for producing a biaryl compound characterized by refluxing a 1,3-dicarbonyl compound, an allyl aldehyde and a 4-methoxy cinnamaldehyde in the presence of Cs 2 CO 3 as a catalyst and toluene as a solvent,
[Reaction Scheme 2]
Figure 112015088834720-pat00014

In the above Reaction Scheme 2,
X is selected from O or NH,
R 1 is selected from the group consisting of C 1 to C 4 alkyl, 4-MeC 6 H 4 -, and 4-ClC 6 H 4 -
R 2 is halogen. 6. The method of claim 5, wherein the biaryl compound is selected from the group consisting of methyl 4- (2-chlorobenzyl) -3-hydroxy-4'- methoxybiphenyl- Hydroxy-4'-methoxybiphenyl-2-carboxylate, 4- (2-chlorobenzyl) -3-hydroxy-4'-methoxy- And 4- (2-chlorobenzyl) -N- (4-chlorophenyl) -3-hydroxy-4'-methoxybiphenyl-2-carboxamide. (Purine-2-yl) -acrylaldehyde or 3- (anthracen-9-yl) acrylaldehyde in the presence of Cs 2 CO 3 as a catalyst and toluene as a solvent, A method for producing a biaryl compound characterized by refluxing a dicarbonyl compound:
[Reaction Scheme 3]
Figure 112015088834720-pat00015

In Scheme 3,
X is selected from O or NH,
R 1 is alkyl, C1 to C4 -CH 2 CH = CH 2 and 4-ClC 6 H 4 - selected from the group consisting of. 8. The method of claim 7, wherein the biaryl compound is selected from the group consisting of (E) -methyl 6- (furan-2-yl) -3- (E) -allyl 6- (furan-2-yl) -3- (3- (furan-2-yl) allyl) -2-hydroxybenzoate, - (3- (furan-2-yl) allyl) -2-hydroxybenzoate, (E) 2-yl) allyl) -2-hydroxybenzamide, (E) -methyl 6- (anthracen-9- Benzoate and (E) -ethyl 6- (anthracene-9-yl) -3- (3- (anthracen-9-yl) allyl) -2-hydroxybenzoate. 3-hydroxybiphenyl-2-carboxylate or 4-cinnamylmethyl-3-hydroxy-N- ( 4-methoxyphenyl) biphenyl-2-carboxamide is hydrogenated.
[Reaction Scheme 4]
Figure 112015088834720-pat00016

In Scheme 4,
R is selected from methoxy or 4-MeOC 6 H 4 NH-. The method according to claim 9, wherein the method for producing a biaryl compound comprises reacting methyl 3-hydroxy-4- (3-phenylpropyl) biphenyl-2-carboxylate and 3-hydroxy-N- (4-methoxyphenyl) 4- (3-phenylpropyl) biphenyl-2-carboxamide. delete delete delete delete
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