KR20160141668A - Novel benzoylcyclohexanedione derivatives and a herbicide comprising the derivatives - Google Patents

Novel benzoylcyclohexanedione derivatives and a herbicide comprising the derivatives Download PDF

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KR20160141668A
KR20160141668A KR1020160067840A KR20160067840A KR20160141668A KR 20160141668 A KR20160141668 A KR 20160141668A KR 1020160067840 A KR1020160067840 A KR 1020160067840A KR 20160067840 A KR20160067840 A KR 20160067840A KR 20160141668 A KR20160141668 A KR 20160141668A
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compound
triazol
benzoyl
ethoxy
methylsulfonyl
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KR101866271B1 (en
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고영관
김은애
이일영
연규환
구동완
류재욱
염현석
곽미영
조숙희
김경애
김낙정
최정섭
서지희
이규양
오승애
김재덕
오태현
최준혁
박성준
홍미숙
정봉진
명을재
김태준
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한국화학연구원
주식회사 팜한농
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N29/00—Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
    • A01N29/10—Halogen attached to an aliphatic side chain of an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system

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  • Pest Control & Pesticides (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

The present invention relates to a novel benzoyl cyclohexanedione compound, a producing method thereof, and an herbicide comprising the compound. The compound of the present invention has high safety for rice crops, has excellent herbicidal activity for gramineous weeds, cyperaceae weeds or broad-leaved weeds, and thus is useful as an herbicide for water surface treatment or foliage treatment.

Description

벤조일사이클로헥산다이온 화합물 및 이 화합물을 포함하는 제초제 {Novel benzoylcyclohexanedione derivatives and a herbicide comprising the derivatives} Benzoylcyclohexanedione derivatives and a herbicide containing the compounds,

본 발명은 신규의 벤조일사이클로헥산다이온 화합물과 이의 제조방법, 그리고 이 화합물을 포함하는 제초제에 관한 것이다.The present invention relates to novel benzoylcyclohexanedione compounds, processes for their preparation, and herbicides comprising these compounds.

일반적으로 제초제는 농작물의 생산성 향상에 매우 중요한 역할을 하는 농자재 중의 하나이며, 이러한 목적으로 그 동안 여러 종류의 제초제들이 개발되어 사용되어 왔다. Generally, herbicides are one of the agricultural materials that plays an important role in improving the productivity of crops. For this purpose, various herbicides have been developed and used for this purpose.

벼 재배용 제초제로서 피라조설퓨론 에틸 (Pyrazosulfuron ethyl)이나 플루세토설퓨론 (Flucetosulfuron) 같은 설포닐우레아계 제초제, 또는 메타미포프 (Metamifop)와 같은 아릴옥시페녹시프로피오네이트계 제초제들이 사용되어 왔다. 밀 재배용 제초제로서 페녹시프롭 에틸 (Phenoxaprop ethyl) 또는 아이오도설퓨런 (Iodosulfuron) 등이 사용되어 왔다. 옥수수 재배용 제초제로서 메조트리온 (Mesotrione)과 같은 트리케톤계 제초제와 니코설퓨런 (Nicosulfuron) 등의 설포닐우레아게 제초제가 개발되어 사용되고 있다. 한편 비선택성 제초제로서는 글라이포세이트 (Glyphosate) 또는 글루포시네이트 (Glufosinate) 등의 제초제들이 사용되어 왔다.As herbicides for rice cultivation, sulfonylurea herbicides such as pyrazosulfuron ethyl and flucetosulfuron, or aryloxyphenoxypropionate herbicides such as metamifop have been used. Phenoxaprop ethyl or Iodosulfuron has been used as a herbicide for wheat cultivation. As a herbicide for corn cultivation, triketone herbicides such as mesotrione and sulfonylurea herbicides such as Nicosulfuron have been developed and used. Herbicides such as glyphosate or glufosinate have been used as non-selective herbicides.

그러나 아직도 농업에 손실을 초래하는 많은 잡초들이 발생하고 있으며, 특히 최근에는 기존 제초제의 장기간 반복사용에 의한 저항성 잡초발생이 문제가 되고 있어, 새로운 제초제의 연구 개발이 계속 요구되고 있다.However, many weeds still cause damage to agriculture, and in recent years, resistance to weeds due to long-term repeated use of existing herbicides has become a problem, and research and development of new herbicides are continuously required.

국제공개특허공보 WO2003-066607호에는 하기 화학식 A로 표시되는 벤조일사이클로헥산다이온 화합물이 개시되어 있다.International Publication No. WO2003-066607 discloses a benzoylcyclohexanedione compound represented by the following formula (A).

[화학식 A](A)

Figure pat00001
Figure pat00001

상기 화학식 A에서, R1은 할로젠원자, 알킬기, 할로알킬기, 알콕시기, 알콕시알킬기 등을 나타내고; m은 0, 1, 2 또는 3을 나타내고; n은 0 또는 1을 나타내고; A는 알킬렌을 나타내고; T는

Figure pat00002
, 또는
Figure pat00003
를 나타내고; R2는 할로젠원자, 알킬기, 알케닐기, 알키닐기, 할로알킬기 또는 페닐기 등을 나타내며, Q는
Figure pat00004
,
Figure pat00005
,
Figure pat00006
,
Figure pat00007
를 나타내고, R3은 하이드록시기, 할로젠원자, 알킬카보닐옥시기, 또는 5 또는 6각의 헤테로아릴싸이오기 등을 나타내고; R4, R5, R6, R7, R8, 및 R9는 서로 독립적으로 할로젠원자 또는 알킬기를 나타내며, R10은 알킬기를 나타내며, R11은 알킬기 또는 사이클로 알킬기를 나타낸다.In the above formula (A), R 1 represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group and the like; m represents 0, 1, 2 or 3; n represents 0 or 1; A represents alkylene; T is
Figure pat00002
, or
Figure pat00003
Lt; / RTI > R 2 represents a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group or a phenyl group, Q represents
Figure pat00004
,
Figure pat00005
,
Figure pat00006
,
Figure pat00007
, R 3 represents a hydroxyl group, a halogen atom, an alkylcarbonyloxy group, a 5-or 6-membered heteroarylthio group, or the like; R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 independently represent a halogen atom or an alkyl group, R 10 represents an alkyl group, and R 11 represents an alkyl group or a cycloalkyl group.

그러나 상기 화학식 A의 화합물은 재배작물에 대한 선택성과 문제 잡초에 대한 방제력 면에서 충분하지 않으므로, 이러한 문제점을 해결할 수 있는 신규 고성능 제초제의 개발이 요구되는 실정이다.
However, the compound of formula (A) is insufficient in terms of selectivity to cultivated crops and problematic control against weeds. Therefore, it is required to develop new high performance herbicides which can solve such problems.

국제공개특허공보 WO2003-066607호, "제초제로 유용한 신규 테트라졸 유도체"WO2003-066607, "New tetrazole derivatives useful as herbicides"

본 발명은 신규 구조의 벤조일사이클로헥산다이온 화합물을 제공하는 것을 목적한다.The present invention seeks to provide novel structures of benzoylcyclohexanedione compounds.

또한, 본 발명은 벤조일사이클로헥산다이온 화합물의 제조방법을 제공하는 것을 다른 목적한다.It is another object of the present invention to provide a process for producing a benzoylcyclohexanedione compound.

또한, 본 발명은 벤조일사이클로헥산다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 화합물이 활성성분으로 포함된 제초제를 제공하는 것을 또 다른 목적한다.
It is still another object of the present invention to provide a herbicide containing a compound selected from the group consisting of benzoylcyclohexanedione compounds and pesticidally acceptable salts thereof as an active ingredient.

상기한 과제 해결을 위한 일 양태에 의하면, 본 발명은 하기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물, 또는 이의 농약학적으로 허용 가능한 염을 그 특징으로 한다 : According to an aspect of the present invention, the present invention provides a benzoylcyclohexanedione compound represented by the following formula (1), or a pesticidally acceptable salt thereof:

[화학식 1][Chemical Formula 1]

Figure pat00008
Figure pat00008

상기 화학식 1에서, In Formula 1,

R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1∼C6알킬) 를 나타내고;R 1 represents a halogen atom, a hydroxyl group, or -OC (O) - (C 1 -C 6 alkyl);

R2 및 R3은 각각 독립적으로 수소원자, 또는 C1∼C6알킬기를 나타내고;R 2 and R 3 are each independently a hydrogen atom or a C 1 -C 6 alkyl group;

R4는 -C1∼C6알킬렌-, -C2∼C6알케닐렌-, -C2∼C6알키닐렌-, C1∼C6할로알킬렌기, -(C1∼C6알킬렌)-O-(C1∼C6알킬렌)-, 또는 -(C1∼C6알킬렌)-S-(C1∼C6알킬렌)-를 나타내고;R 4 is -C 1 -C 6 alkylene-, -C 2 -C 6 alkenylene-, -C 2 -C 6 alkynylene-, C 1 -C 6 haloalkylene group, - (C 1 -C 6 alkyl alkylene) -O- (C 1 ~C 6 alkylene) -, or - (C 1 ~C 6 alkylene) -S- (C 1 ~C 6 alkylene) - represents;

X는 할로젠원자, 또는 C1∼C6알킬기를 나타내고;X represents a halogen atom, or a C 1 -C 6 alkyl group;

Y는 -NO2, 또는 -S(O)2-(C1∼C2알킬)를 나타내고;Y represents -NO 2 , or -S (O) 2 - (C 1 -C 2 alkyl);

Z는

Figure pat00009
,
Figure pat00010
또는
Figure pat00011
로부터 선택되고,Z is
Figure pat00009
,
Figure pat00010
or
Figure pat00011
≪ / RTI >

R5는 수소원자, 할로젠원자, C1∼C6알킬기, 또는 C1∼C6할로알킬기를 나타내고;R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, or a C 1 -C 6 haloalkyl group;

n은 0, 1, 또는 2의 정수를 나타낸다.
n represents an integer of 0, 1, or 2;

본 발명의 다른 양태에 따르면, 본 발명은 상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 1종 이상의 활성화합물 0.1 중량% 내지 99.9 중량%; 및 계면활성제와 고체 또는 액체 희석제로 이루어진 군으로부터 선택된 1종 이상의 첨가제 0.1 중량% 내지 99.9 중량%;포함된 제초제 조성물을 그 특징으로 한다.
According to another aspect of the present invention, the present invention provides a composition comprising 0.1% by weight to 99.9% by weight of at least one active compound selected from the group consisting of the benzoylcyclohexanedione compounds represented by Formula 1 and the pesticidally acceptable salts thereof; And 0.1% to 99.9% by weight of at least one additive selected from the group consisting of surfactants and solid or liquid diluents.

본 발명의 다른 양태에 따르면, 본 발명은 상기 제초제 조성물을 수면처리 또는 경엽처리하여 잡초를 방제하는 방법을 그 특징으로 한다.
According to another aspect of the present invention, there is provided a method for controlling weeds by treating the herbicidal composition with a water or a foliar treatment.

본 발명의 또 다른 양태에 따르면, 본 발명은 하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시 벤조에이트와 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약을 반응시켜, R1이 하이드록시기인 하기 화학식 1a로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법을 그 특징으로 한다. According to still another aspect of the present invention, there is provided a process for the preparation of 3-oxo-1-cycloalkenyl-3-alkoxybenzoate by reacting 3-oxo-1-cycloalkenyl-3-alkoxybenzoate represented by the following general formula 2 with acetone cyanohydrin reagent represented by general formula 1 > is a hydroxy group, the benzoylcyclohexanedione compound represented by the following formula (1a).

Figure pat00012
Figure pat00012

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같다)
(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are each as defined in the above formula (1)

본 발명의 또 다른 양태에 따르면, 본 발명은 R1이 하이드록시기인 상기 화학식 1a로 표시되는 화합물을 할로젠화 시약과 반응시켜, R1이 할로젠원자인 하기 화학식 1b로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법을 그 특징으로 한다. In accordance with another aspect of the invention, the present invention R 1 is hydroxyl group is reacted with a halogenated reagent to the compound represented by Formula 1a, to a halogen atom is R 1 hexane benzoyl cycloalkyl of the formula 1b And a method for producing a polyionic compound.

Figure pat00013
Figure pat00013

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같고, Hal.은 할로젠원자를 나타낸다)
(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1 and Hal represents a halogen atom,

본 발명의 또 다른 양태에 따르면, 본 발명은 R1이 하이드록시기인 상기 화학식 1a로 표시되는 화합물을 R6-C(O)-Cl로 표시되는 알킬카르보닐 클로라이드와 반응시켜, R1이 알킬카르보닐옥시기인 하기 화학식 1c로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법을 그 특징으로 한다. In accordance with another aspect of the invention, by the present invention, R 1 is hydroxyl group reacted with an alkyl carbonyl chloride represented by the compound represented by the above formula (1a) with R 6 -C (O) -Cl, R 1 is an alkyl And a method for producing a benzoylcyclohexane-dione compound represented by the following formula (1c) which is a carbonyloxy group.

Figure pat00014
Figure pat00014

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같고, R6는 C1∼C4알킬기를 나타낸다.)
(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in the above formula (1), and R 6 represents a C 1 -C 4 alkyl group.

본 발명에 따른 신규 화합물은 우수한 작물선택성과 제초활성을 나타낸다. 특히 벼에 대한 안전성이 우수하면서 수면처리 또는 경엽처리에서 화본과 잡초, 사초과 잡초, 또는 광엽 잡초의 제거 효과가 뛰어나므로 선택성 제초제로 유용하다.The novel compounds according to the invention exhibit excellent crop selection and herbicidal activity. Especially, it is useful as a selective herbicide because it has excellent safety against rice and is excellent in the effect of removing weeds, weeds, weeds and light weeds in water treatment or foliar treatment.

이와 같은 본 발명을 보다 구체적으로 설명하면 하기와 같다.Hereinafter, the present invention will be described in more detail.

본 발명은 하기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물 및 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 화합물에 관한 것이다.The present invention relates to compounds selected from the group consisting of benzoylcyclohexanedione compounds represented by the following formula (1) and pesticidally acceptable salts.

[화학식 1][Chemical Formula 1]

Figure pat00015
Figure pat00015

상기 화학식 1에서, In Formula 1,

R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1∼C6알킬) 를 나타내고;R 1 represents a halogen atom, a hydroxyl group, or -OC (O) - (C 1 -C 6 alkyl);

R2 및 R3은 각각 독립적으로 수소원자, 또는 C1∼C6알킬기를 나타내고;R 2 and R 3 are each independently a hydrogen atom or a C 1 -C 6 alkyl group;

R4는 -C1∼C6알킬렌-, -C2∼C6알케닐렌-, -C2∼C6알키닐렌-, C1∼C6할로알킬렌기, -(C1∼C6알킬렌)-O-(C1∼C6알킬렌)-, 또는 -(C1∼C6알킬렌)-S-(C1∼C6알킬렌)-를 나타내고;R 4 is -C 1 -C 6 alkylene-, -C 2 -C 6 alkenylene-, -C 2 -C 6 alkynylene-, C 1 -C 6 haloalkylene group, - (C 1 -C 6 alkyl alkylene) -O- (C 1 ~C 6 alkylene) -, or - (C 1 ~C 6 alkylene) -S- (C 1 ~C 6 alkylene) - represents;

X는 할로젠원자, 또는 C1∼C6알킬기를 나타내고;X represents a halogen atom, or a C 1 -C 6 alkyl group;

Y는 -NO2, 또는 -S(O)2-(C1∼C2알킬)를 나타내고;Y represents -NO 2 , or -S (O) 2 - (C 1 -C 2 alkyl);

Z는

Figure pat00016
,
Figure pat00017
또는
Figure pat00018
로부터 선택되고,Z is
Figure pat00016
,
Figure pat00017
or
Figure pat00018
≪ / RTI >

R5는 수소원자, 할로젠원자, C1∼C6알킬기, 또는 C1∼C6할로알킬기를 나타내고;R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, or a C 1 -C 6 haloalkyl group;

n은 0, 1, 또는 2의 정수를 나타낸다.n represents an integer of 0, 1, or 2;

상기 화학식 1로 표시되는 화합물에 있어, 바람직하게는 In the compound represented by the general formula (1), preferably

기 R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1∼C4알킬)를 나타내고;Group R 1 is a halogen atom, a hydroxyl group, or -OC (O) - represents a (C 1 ~C 4 alkyl);

상기 R2 및 R3은 각각 독립적으로 수소원자, 메틸기, 에틸기, 노말프로필기, 또는 이소프로필기를 나타내고;Each of R 2 and R 3 independently represents a hydrogen atom, a methyl group, an ethyl group, a normal propyl group or an isopropyl group;

상기 R4는 -C1∼C4알킬렌-, -C2∼C4알케닐렌-, -C2∼C4알키닐렌-, -C1∼C4할로알킬렌-, -(C1∼C4알킬렌)-O-CH2-, -(C1∼C4알킬렌)-O-CH2CH2-, -(C1∼C4알킬렌)-S-CH2-, 또는 -(C1∼C4알킬렌)-S-CH2CH2- 를 나타내고; Wherein R 4 is -C 1 ~C 4 alkylene -, -C 2 ~C 4 alkenylene -, -C 2 ~C 4 alkynylene -, -C 1 ~C 4 haloalkyl alkylene -, - (C 1 ~ C 4 alkylene) -O-CH 2 -, - (C 1 ~C 4 alkylene) -O-CH 2 CH 2 - , - (C 1 ~C 4 alkylene) -S-CH 2 -, or - (C 1 -C 4 alkylene) -S-CH 2 CH 2 -;

상기 X는 할로젠원자, 또는 C1∼C4알킬기를 나타내고;X represents a halogen atom, or a C 1 -C 4 alkyl group;

상기 Y는 -NO2, 또는 -S(O)2-CH3 를 나타내고;Wherein Y is -NO 2, Or -S (O) -CH 3 represents a 2;

상기 Z는

Figure pat00019
,
Figure pat00020
또는
Figure pat00021
로부터 선택되고,Z is
Figure pat00019
,
Figure pat00020
or
Figure pat00021
≪ / RTI >

상기 R5는 수소원자, 할로젠원자, C1∼C4알킬기, 또는 C1∼C4할로알킬기를 나타내고;R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, or a C 1 -C 4 haloalkyl group;

상기 n은 0, 1, 또는 2의 정수를 나타내는 화합물의 경우이다.
And n is a compound representing an integer of 0, 1, or 2.

상기 화학식 1로 표시되는 화합물에 있어, 보다 바람직하게는In the compound represented by the general formula (1), more preferably

상기 R1은 클로로원자, 하이드록시기, 또는 -O-C(O)-(C1∼C4알킬)를 나타내고;Wherein R 1 represents a chloro atom, a hydroxy group, or -OC (O) - (C 1 -C 4 alkyl);

상기 R2 및 R3은 각각 독립적으로 수소원자, 또는 메틸기를 나타내고;Each of R 2 and R 3 independently represents a hydrogen atom or a methyl group;

상기 R4는 -C1∼C4알킬렌-, -C2∼C4알케닐렌-, -C2∼C4알키닐렌-, -C1∼C2할로알킬렌-, -(C1∼C2알킬렌)-O-CH2-, -(C1∼C2알킬렌)-O-CH2CH2-, -(C1∼C2알킬렌)-S-CH2-, 또는 -(C1∼C2알킬렌)-S-CH2CH2- 를 나타내고;Wherein R 4 is -C 1 ~C 4 alkylene -, -C 2 ~C 4 alkenylene -, -C 2 ~C 4 alkynylene -, -C 1 ~C 2 haloalkoxy alkylene -, - (C 1 ~ C 2 alkylene) -O-CH 2 -, - (C 1 ~C 2 alkylene) -O-CH 2 CH 2 - , - (C 1 ~C 2 alkylene) -S-CH 2 -, or - (C 1 -C 2 alkylene) -S-CH 2 CH 2 -;

상기 X는 클로로원자, 또는 메틸기를 나타내고;X represents a chloro atom, or a methyl group;

상기 Y는 -NO2, 또는 -S(O)2-CH3를 나타내고;Wherein Y is -NO 2, Or -S (O) -CH 3 represents a 2;

상기 Z는

Figure pat00022
,
Figure pat00023
,
Figure pat00024
,
Figure pat00025
,
Figure pat00026
, 또는
Figure pat00027
를 나타내고;Z is
Figure pat00022
,
Figure pat00023
,
Figure pat00024
,
Figure pat00025
,
Figure pat00026
, or
Figure pat00027
Lt; / RTI >

상기 n은 0, 또는 2의 정수를 나타내는 화합물의 경우이다.
Wherein n is 0 or an integer of 2.

상기 화학식 1로 표시되는 화합물에 있어, 보다 더 바람직하게는 In the compound represented by the general formula (1), more preferably

상기 R1은 클로로원자, 하이드록시기, 또는 -O-C(O)-(C1∼C4알킬)를 나타내고;Wherein R 1 represents a chloro atom, a hydroxy group, or -OC (O) - (C 1 -C 4 alkyl);

상기 R2 및 R3은 각각 독립적으로 수소원자, 또는 메틸기를 나타내고;Each of R 2 and R 3 independently represents a hydrogen atom or a methyl group;

상기 R4는 -CH2-, -(CH2)2-, -(CH2)3-, -CH2CH(CH3)-, -(CH2)4-, -CH2CH(CH3)CH2-, -(CH2)5-, -CH2C(CH3)2CH2-, cis -CH2CH=CHCH2-, trans -CH2CH=CHCH2-, -CH2C≡CCH2-, -CH2CHF-, -CH2-O-CH2-, -(CH2)2-O-CH2-, -CH2-O-(CH2)2-, -(CH2)2-O-(CH2)2-, -CH2-S-CH2-, -(CH2)2-S-CH2-, -CH2-S-(CH2)2-, 또는 -(CH2)2-S-(CH2)2-를 나타내고;Wherein R 4 is -CH 2 -, - (CH 2 ) 2 -, - (CH 2) 3 -, -CH 2 CH (CH 3) -, - (CH 2) 4 -, -CH 2 CH (CH 3 ) CH 2 -, - (CH 2) 5 -, -CH 2 C (CH 3) 2 CH 2 -, cis -CH 2 CH = CHCH 2 -, trans -CH 2 CH = CHCH 2 -, -CH 2 C ≡CCH 2 -, -CH 2 CHF-, -CH 2 -O-CH 2 -, - (CH 2) 2 -O-CH 2 -, -CH 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -, -CH 2 -S-CH 2 -, - (CH 2) 2 -S-CH 2 -, -CH 2 -S- (CH 2) 2 -, or - (CH 2 ) 2 -S- (CH 2 ) 2 -;

상기 X는 클로로원자, 또는 메틸기를 나타내고;X represents a chloro atom, or a methyl group;

상기 Y는 -NO2, 또는 -S(O)2-CH3를 나타내고;Wherein Y is -NO 2, Or -S (O) -CH 3 represents a 2;

상기 Z는

Figure pat00028
,
Figure pat00029
또는
Figure pat00030
를 나타내고;Z is
Figure pat00028
,
Figure pat00029
or
Figure pat00030
Lt; / RTI >

상기 n은 0 또는 2의 정수를 나타내는 화합물의 경우이다.
Wherein n is 0 or an integer of 2.

상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물을 구체적으로 예시하면 하기와 같다 : Specific examples of the benzoylcyclohexane-dione compound represented by the formula (1) are as follows:

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 2); 2- (3- (2- (2 H- 1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 2);

2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 4); 2- (3- (4- (2 H- 1,2,3- triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 4);

2-(3-(2-(1H-1,2,3-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 7); 2- (3- (2- (1 H- 1,2,3- triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 7);

2-(3-(4-(1H-1,2,3-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 9); 2- (3- (4- (1 H- 1,2,3- triazol-1-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 9);

2-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 12); 2- (3- (2- (1 H- 1,2,4- triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 12);

3-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 27); 3- (3- (2- (1 H- 1,2,4- triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4-hydroxy-bicyclo [ 3.2.1] ox-3-en-2-one (Compound No. 27);

2-(3-(2-(3-브로모-1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 32);() -2-chloro-4- (methylsulfonyl) 3- (2- (3-bromo -1 H -1,2,4- triazol-1-yl) benzoyl) -3-2- 2-en-1-one (Compound No. 32);

2-(3-(2-((1H-1,2,3-트리아졸-1-일)메톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 35);2- (3- (2 - (( 1 H- 1,2,3- triazol-1-yl) methoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy 2-en-1-one (Compound No. 35);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 41); 2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 41);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 44);2- (3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoyl) -3-hydroxycyclohexyl- One (Compound No. 44);

2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 48);2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) Benzoyl) -3-hydroxycyclohexyl-2-en-1-one (Compound No. 48);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 61);() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 - hydroxybicyclo [3.2.1] oct-3-en-2-one (Compound No. 61);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 아세테이트 (화합물번호 62);() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 - oxobicyclo [3.2.1] oct-2-yl-2-yl acetate (Compound No. 62);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 사이클로프로판카르복실레이트 (화합물번호 63);() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 -Oxobicyclo [3.2.1] oct-2-yl) -2-ylcyclopropanecarboxylate (Compound No. 63);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 67);(3-ethoxy (ethoxy-2- (2 H -1,2,3- triazol-2-yl))) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo Hept-1-en-1-yl acetate (Compound No. 67);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 사이클로프로판카르복실레이트 (화합물번호 68);(3-ethoxy (ethoxy-2- (2 H -1,2,3- triazol-2-yl))) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo Hex-1-en-1-yl cyclopropanecarboxylate (Compound No. 68);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아이소부티레이트 (화합물번호 69);(3-ethoxy (ethoxy-2- (2 H -1,2,3- triazol-2-yl))) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo 1-en-1-ylisobutyrate (Compound No. 69);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 피발레이트 (화합물번호 70);(3-ethoxy (ethoxy-2- (2 H -1,2,3- triazol-2-yl))) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo Hex-1-sen-1-yl pivalate (Compound No. 70);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 71); 2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-cyclohexyl -1 -Acen-1-yl acetate (Compound No. 71);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 91);() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 2-3 -Cyclohex-2-en-1-one (Compound No. 91);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 94);() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 -Chlorobiscyclo [3.2.1] oct-3-en-2-one (Compound No. 94);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 96);3- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -4-chloro-by Cyclo [3.2.1] ox-3-en-2-one (Compound No. 96);

2-(3-(2-(1H-1,2,3-트리아졸-1-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 101);(Ethoxy-3- (2- (1 H -1,2,3- triazol-1-yl) ethoxy)) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo Hept-1-en-1-yl acetate (Compound No. 101);

2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아이소부티레이트 (화합물번호 104);2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) Benzoyl) -3-oxocyclohexyl-1-sen-1-ylisobutyrate (Compound No. 104);

2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-플루오로사이클로헥-2-센-1-온 (화합물번호 118); 2- (3- (3- (2 H -1,2,3- triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-fluoro-cyclohexyl- 2-en-1-one (Compound No. 118);

2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-브로모사이클로헥-2-센-1-온 (화합물번호 119); 2- (3- (3- (2 H -1,2,3- triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-bromo-cyclohexyl- 2-en-1-one (Compound No. 119);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 120);2- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) benzoyl-2-methyl-4-nitro) -3-hydroxy Cyclohex-2-en-1-one (Compound No. 120);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 121);2- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-methyl-4-nitro-benzoyl) -3-oxo-bicyclo 1-yl-acetate (Compound No. 121);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 123);2- (3- (2- (2- (H 2 -1,2,3- triazine-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Hydroxycyclohex-2-en-1-one (Compound No. 123);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 124);2- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Oxocyclohexyl-1-en-1-yl acetate (Compound No. 124);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온(화합물번호 125);2- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Cyclohex-2-en-1-one (Compound No. 125);

3-클로로-2-(3-(2-플루오로-2-(1H-1,2,3-트리아졸-1-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)사이클로헥-2-센-1-온 (화합물번호 133);(3-chloro-2- (3- (2-fluoro-2- (1 H -1,2,3- triazol- 1 -yl) Cyclohex-2-en-1-one (Compound No. 133);

3-클로로-2-(3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)사이클로헥-2-센-1-온 (화합물번호 135);3-chloro-2- (3- (2-methyl-4- (methylsulfonyl) to 2- (2 H -1,2,3- triazol-2-yl) 2-fluoro-benzoyl) Cyclohex-2-en-1-one (Compound No. 135);

2-(3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 136); 및2- (3- (2-methyl-4- (methylsulfonyl) on -2- (2 H -1,2,3- triazol-2-yl) 2-fluoro-benzoyl) -3-oxo Cyclohex-1-en-1-yl acetate (Compound No. 136) and

농약학적으로 허용 가능한 이들의 염으로 이루어진 군으로부터 선택된 화합물.
Lt; RTI ID = 0.0 > pharmaceutically < / RTI > acceptable salts thereof.

또한, 본 발명에 따른 상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물은 농약학적으로 허용 가능한 염의 형태로 사용될 수 있다. 농약학적으로 허용 가능한 염이라 함은, 예를 들어, 금속염, 유기 염기와의 염, 무기산과의 염, 유기산과의 염, 염기성, 또는 산성 아미노산과의 염 등이 포함될 수 있다. 적합한 금속염은, 예를 들어, 나트륨염, 칼륨염 등과 같은 알칼리 금속염; 칼슘염, 마그네슘염, 바륨염 등과 같은 알칼리 토금속염; 알루미늄염 등이 포함될 수 있다. 유기 염기와의 염은, 예를 들어, 트리메틸아민, 트리에틸아민, 다이이소프로필에틸아민, 피리딘, 피콜린, 2,6-루티딘, 에탄올아민, 다이에탄올아민, 트리에탄올아민, 사이클로헥실아민, 다이사이클로헥실아민, N,N-다이벤질에틸렌다이아민 등으로부터 선택된 염기와의 염이 포함될 수 있다. 무기산과의 염은, 예를 들어, 염산, 브롬화수소산, 질산, 황산, 인산 등으로부터 선택된 무기산과의 염이 포함될 수 있다. 유기산과의 염은, 예를 들어, 포름산, 아세트산, 트리플루오로아세트산, 프탈산, 푸마르산, 옥살산, 타르타르산, 말레인산, 시트르산, 숙신산, 메탄술폰산, 벤젠술폰산, p-톨루엔술폰산 등으로부터 선택된 유기산과의 염이 포함될 수 있다. 염기성 아미노산과의 염은, 예를 들어, 알기닌, 라이신, 오르니틴 등으로부터 선택된 염기성 아미노산과의 염이 포함될 수 있다. 산성 아미노산과의 염은, 예를 들어, 아스파르트산, 글루탐산 등으로부터 선택된 산성 아미노산과의 염이 포함될 수 있다.The benzoylcyclohexane-dione compound represented by Formula 1 according to the present invention may be used in the form of a pesticide acceptable salt. The pesticidally acceptable salt may include, for example, a metal salt, a salt with an organic base, a salt with an inorganic acid, a salt with an organic acid, a salt with a basic or acidic amino acid, and the like. Suitable metal salts include, for example, alkali metal salts such as sodium salts, potassium salts and the like; Alkaline earth metal salts such as calcium salts, magnesium salts, barium salts and the like; Aluminum salts and the like. Salts with organic bases include, for example, salts with organic bases such as trimethylamine, triethylamine, diisopropylethylamine, pyridine, picoline, 2,6-lutidine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine, Dicyclohexylamine, N, N -dibenzylethylenediamine , and the like. Salts with inorganic acids may include, for example, salts with inorganic acids selected from hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid and the like. The salt with an organic acid is a salt with an organic acid selected from, for example, formic acid, acetic acid, trifluoroacetic acid, phthalic acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, citric acid, succinic acid, methanesulfonic acid, benzenesulfonic acid, p- May be included. The salt with a basic amino acid may include a salt with a basic amino acid selected from, for example, arginine, lysine, ornithine, and the like. The salt with an acidic amino acid may include a salt with an acidic amino acid selected from, for example, aspartic acid, glutamic acid and the like.

또한, 본 발명에 따른 상기 화학식 1로 표시되는 화합물 중 일부는 수성 및 유기 용매와 같은 용매로부터 결정화되거나 또는 재결정화될 수 있다. 이러한 경우, 상기 화학식 1로 표시되는 화합물은 용매화물을 형성할 수 있다. 동결건조와 같은 방법으로 제조 가능한 다양한 양의 물 함유 화합물 이외에 수화물을 비롯한 화학 양론적 용매화물도 본 발명의 범위에 속한다.In addition, some of the compounds represented by Formula 1 according to the present invention may be crystallized or recrystallized from a solvent such as aqueous and organic solvents. In this case, the compound represented by Formula 1 may form a solvate. In addition to various amounts of water-containing compounds that can be prepared by methods such as lyophilization, stoichiometric solvates, including hydrates, are also within the scope of the present invention.

또한, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 하나 또는 그 이상의 비대칭 중심을 가질 수 있고, 이러한 화합물의 경우 거울상 이성체 또는 부분입체이성체가 존재할 수 있다. 따라서 본 발명은 각 이성체 또는 이들 이성체 혼합물을 포함한다.In addition, the compound represented by Formula 1 according to the present invention may have one or more asymmetric centers, and in the case of such a compound, an enantiomer or diastereomer may exist. Accordingly, the present invention includes each isomer or mixture of these isomers.

또한, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 토토머 형태로도 존재가 가능한 바, 본 발명은 각 토토머 또는 이들의 혼합물 역시 포함한다. In addition, the compound represented by Formula 1 according to the present invention may exist in the form of a tautomer, and the present invention also includes each tautomer or a mixture thereof.

또한, 본 발명에 따른 화합물을 나타내기 위해 사용된 치환기에 대한 구체적으로 설명하면 하기와 같다. In addition, the substituent used to represent the compound according to the present invention will be described in detail as follows.

본 발명에서의 '할로' 또는 '할로젠'이란 용어는 서로 교환 가능하게 사용될 수 있다. 구체적으로는 염소, 불소, 요오드 및 브롬으로부터 유도된 라디칼 등이 포함될 수 있다.The terms " halo " or " halogen " in the present invention may be used interchangeably. Specifically, radicals derived from chlorine, fluorine, iodine, and bromine may be included.

본 발명에서의 '알킬'은 탄소원자가 1개 내지 6개(바람직하기로는 1개 내지 4개) 포함된 직쇄, 분지쇄, 또는 고리쇄를 이루는 포화탄화수소 라디칼을 의미한다. 구체적으로는 메틸, 에틸, 노말프로필, 이소프로필, 사이클로프로필, 노말부틸, sec-부틸, tert-부틸, 노말펜틸, 이소펜틸, 사이클로펜틸, 노말헥실, 2-(메틸)펜틸, 사이클로헥실 등이 포함될 수 있다.'Alkyl' in the present invention means a saturated hydrocarbon radical having a straight, branched or cyclic chain containing 1 to 6 (preferably 1 to 4) carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec -butyl, tert -butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, 2- .

본 발명에서의 '할로알킬'은 할로젠원자가 1개 내지 10개 치환된 알킬 라디칼을 의미한다. 구체적으로는 트리플로로메틸, 다이클로로에틸 등이 포함될 수 있다.In the present invention, "haloalkyl" means an alkyl radical substituted with 1 to 10 halogen atoms. Specific examples thereof include trifluoromethyl, dichloroethyl and the like.

본 발명에서의 '알콕시'는 O-알킬으로서, 예를 들면 메톡시, 에톡시, 노말프로폭시, 이소프로폭시, 노말부톡시, sec-부톡시, t-부톡시 등이 포함될 수 있다.
'Alkoxy' in the present invention is O-alkyl and may include, for example, methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, sec -butoxy, t -butoxy and the like.

한편, 본 발명은 상기 화학식 1로 표시되는 벤조일사이클로헥사다이온 화합물의 제조방법을 포함한다. The present invention also includes a process for preparing benzoylcyclohexadarone compounds represented by Formula 1 above.

본 발명에 따른 제조방법에 의하면, 하기 반응식 1에 나타난 바와 같이, According to the production method of the present invention, as shown in the following Reaction Scheme 1,

하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시벤조에이트를 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약과 반응시켜, R1이 하이드록시기인 하기 화학식 1a로 표시되는 벤조일사이클로헥사다이온 화합물을 제조하는 과정; 을 수행하여 벤조일사이클로헥사다이온 화합물을 제조할 수 있다.To make the 3-oxo-1-cycloalkenyl-3-alkoxy benzoate represented by the formula (2) reacting a reagent of acetone gave a cyano nohayi represented by the formula 3, R 1 is hydroxyl group represented by the formula (1a) benzoyl A process for preparing a cyclohexadione compound; To produce a benzoylcyclohexadione compound.

[반응식 1][Reaction Scheme 1]

Figure pat00031
Figure pat00031

(상기 반응식 1에서 R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같다)(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in the above formula (1)

상기 반응식 1에 따른 제조방법은 시안화 화합물과 염기 조건 하에서 수행될 수 있다. 상기 시안화 화합물로는 구체적으로 시안화 나트륨, 시안화 칼륨, 아세톤 시아나이드, 수소화 시아나이드 등으로부터 선택된 1종 이상이 사용될 수 있다. 그리고 염기는 트리에틸아민, 다이이소프로필에틸아민의 지방족 아민류, 다이메틸아닐린 등의 방향족 아민류, 피리딘 등이 포함되는 유기 염기일 수 있고, 또는 탄산리튬, 탄산나트륨, 탄산칼륨 등의 알칼리금속 카보네이트와 같은 무기 염기를 사용할 수 있다. 상기 염기는 1종 또는 2종 이상을 혼합 사용할 수도 있다. 시안화 화합물과 염기의 사용량에 있어서는, 상기 화학식 2로 표시되는 화합물 1 몰을 기준으로 각각 1 ∼ 4 몰비 범위로 사용될 수 있고, 바람직하기로는 1 ∼ 2 몰비 범위로 사용될 수 있다. The preparation method according to Reaction Scheme 1 can be carried out under a cyanide compound and a base. Specific examples of the cyanide compound include at least one selected from the group consisting of sodium cyanide, potassium cyanide, acetone cyanide, and hydrogenated cyanide. The base may be an organic base containing triethylamine, diisopropylethylamine, aliphatic amines such as diisopropylethylamine, aromatic amines such as dimethyl aniline, pyridine, etc., or an alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate An inorganic base can be used. These bases may be used alone or in combination of two or more. The cyanide compound and the base may be used in an amount of 1 to 4 molar times, preferably 1 to 2 molar times, based on 1 mol of the compound represented by the formula (2).

반응온도는 -10℃ 내지 80℃ 범위에서 가능하며, 바람직하게는 5℃ 내지 40℃의 온도를 유지한다. 반응용매로는 당 분야에서 사용되어 온 통상의 유기용매는 모두 사용될 수 있으며 이의 선택에 특별한 제한을 두지 않는다. 반응용매를 구체적으로 예시하면 톨루엔, 다이클로로메탄, 클로로포름, 1,2-다이클로로에탄, 다이에틸 에테르, 다이메톡시에탄, 테트라하이드로퓨란, 아세톤, 아세토나이트릴, 에틸 아세테이트, 다이메틸포름아마이드 등이 포함될 수 있다. 반응이 종료된 후에는 유기용매로 희석하여 산으로 세척하고 얻어진 유기층을 건조, 농축하고 칼럼크로마토그래피로 정제할 수 있다.
The reaction temperature is in the range of -10 DEG C to 80 DEG C, preferably in the range of 5 DEG C to 40 DEG C. As the reaction solvent, any conventional organic solvent which has been used in the art can be used and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent include toluene, dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, dimethoxyethane, tetrahydrofuran, acetone, acetonitrile, ethyl acetate, dimethylformamide May be included. After completion of the reaction, the reaction mixture is diluted with an organic solvent, washed with an acid, and the obtained organic layer is dried, concentrated and purified by column chromatography.

또한 본 발명에 따른 제조방법에 의하면, 하기 반응식 2에 나타난 바와 같이, Further, according to the production method of the present invention, as shown in the following Reaction Scheme 2,

a)하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시벤조에이트를 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약과 반응시켜, R1이 하이드록시기인 하기 화학식 1a로 표시되는 화합물을 제조하는 과정; 및 a) to make the 3-oxo-1-cycloalkenyl-3-alkoxy benzoate represented by the formula (2) reacting a reagent of acetone gave a cyano nohayi represented by the formula 3, R 1 is hydroxyl group represented by the formula (1a) ≪ / RTI > And

b-1)하기 화학식 1a로 표시되는 화합물을 할로젠화 시약과 반응시켜, R1이 할로젠원자인 하기 화학식 1b로 표시되는 벤조일사이클로헥사다이온 화합물을 제조하는 과정; 을 수행하여 벤조일사이클로헥사다이온 화합물을 제조할 수 있다.b-1) reacting a compound represented by the formula (1a) with a halogenating reagent to prepare a benzoylcyclohexadaion compound represented by the formula (1b) wherein R 1 is a halogen atom; To produce a benzoylcyclohexadione compound.

[반응식 2][Reaction Scheme 2]

Figure pat00032
Figure pat00032

(상기 반응식 1에서 R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같고, Hal.은 할로젠원자를 나타낸다)(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in the above formula (1) and Hal represents a halogen atom,

상기 반응식 2에 따른 제조방법은 a)상기 반응식 1에 따른 제조방법으로 상기 화학식 1a로 표시되는 화합물을 얻는 과정 및 b-1)상기 화학식 1a로 표시되는 화합물을 할로젠화 하는 과정으로 이루어진다.The process according to Reaction Scheme 2 a) comprises the steps of: a) obtaining the compound of Formula 1a by the process of Scheme 1; and b-1) halogenating the compound of Formula 1a.

상기 할로젠화 과정은 통상의 유기용매 조건 하에서 할로젠화 시약을 사용하여 수행할 수 있다. 상기 할로젠화 시약으로는 구체적으로 옥살릴클로라이드, 옥살릴브로마이드, 다이에틸아미노설퍼 트라이플루오라이드 등으로부터 선택된 1종 이상이 사용될 수 있다. 할로젠화 시약의 사용량에 있어서는 상기 화학식 1a로 표시되는 화합물 1 몰을 기준으로 1 ∼ 3 몰비 범위로 사용될 수 있고, 바람직하기로는 1 ∼ 1.5 몰비 범위로 사용될 수 있다.  The above-described halogenation can be carried out using a halogenating reagent under ordinary organic solvent conditions. Specific examples of the halogenating reagent include at least one selected from oxalyl chloride, oxalyl bromide, diethylaminosulfur trifluoride, and the like. The halogenating reagent may be used in an amount of 1 to 3 molar equivalents, preferably 1 to 1.5 molar equivalents, based on 1 mol of the compound represented by the formula (1a).

상기 할로젠화 반응온도는 0℃ 내지 40℃ 범위에서 가능하며, 상온을 유지하는 것이 보다 바람직하다. 반응용매로는 당 분야에서 사용되어 온 통상의 유기용매는 모두 사용될 수 있으며 이의 선택에 특별한 제한을 두지 않는다. 반응용매를 구체적으로 예시하면 다이클로로메탄, 클로로포름, 1,2-다이클로로에탄 등이 사포함될 수 있다. 반응이 종료된 후에는 유기용매로 희석하여 물로 세척하고 얻어진 유기층을 건조, 농축하고 칼럼크로마토그래피로 정제할 수 있다.
The halogenation reaction temperature is in the range of 0 ° C to 40 ° C, and it is more preferable to maintain the room temperature. As the reaction solvent, any conventional organic solvent which has been used in the art can be used and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent include dichloromethane, chloroform, 1,2-dichloroethane, and the like. After completion of the reaction, the reaction mixture is diluted with an organic solvent, washed with water, and the obtained organic layer is dried, concentrated and purified by column chromatography.

또한 본 발명에 따른 제조방법에 의하면, 하기 반응식 3에 나타난 바와 같이, Further, according to the production method of the present invention, as shown in the following Reaction Scheme 3,

a)하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시벤조에이트를 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약과 반응시켜, R1이 하이드록시기인 하기 화학식 1a로 표시되는 화합물을 제조하는 과정; 및 a) to make the 3-oxo-1-cycloalkenyl-3-alkoxy benzoate represented by the formula (2) reacting a reagent of acetone gave a cyano nohayi represented by the formula 3, R 1 is hydroxyl group represented by the formula (1a) ≪ / RTI > And

b-2)하기 화학식 1a로 표시되는 화합물을 하기 화학식 4로 표시되는 알킬카르보닐 클로라이드 시약과 반응시켜, R1이 알킬카르보닐옥시기인 하기 화학식 1c로 표시되는 벤조일사이클로헥사다이온 화합물을 제조하는 과정; 을 수행하여 벤조일사이클로헥사다이온 화합물을 제조할 수 있다.b-2) reacting a compound represented by the following formula (1a) with an alkylcarbonyl chloride reagent represented by the following formula (4) to prepare a benzoylcyclohexadairion compound represented by the following formula (1c) wherein R 1 is an alkylcarbonyloxy group process; To produce a benzoylcyclohexadione compound.

[반응식 3][Reaction Scheme 3]

Figure pat00033
Figure pat00033

(상기 반응식 3에서 R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같고, R6은 C1∼C4알킬기를 나타낸다.)(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in the above formula (1) and R 6 represents a C 1 -C 4 alkyl group.

상기 반응식 3에 따른 제조방법은 a)상기 반응식 1에 따른 제조방법으로 상기 화학식 1a로 표시되는 화합물을 얻는 과정 및 b-2)상기 화학식 1a로 표시되는 화합물을 알킬카르보닐화 하는 과정으로 이루어진다.The process according to Reaction Scheme 3 comprises the steps of: a) obtaining the compound of Formula 1a by the process of Reaction Scheme 1; and b-2) alkylcarbonylating the compound of Formula 1a.

상기 알킬카르보닐화 과정은 알킬카르보닐 클로라이드와 염기 조건 하에서 수행될 수 있다. 상기 알킬카르보닐 클로라이드는 구체적으로 아세틸 클로라이드, 프로피오닐 클로라이드, 부티릴 클로라이드 등이 포함될 수 있다. 상기 염기는 트리에틸아민, 다이이소프로필에틸아민의 지방족 아민류, 다이메틸아닐린 등의 방향족 아민류, 피리딘 등이 포함되는 유기 염기일 수 있고, 또는 탄산리튬, 탄산나트륨, 탄산칼륨 등의 알칼리금속 카보네이트와 같은 무기 염기를 사용할 수 있다. 상기 염기는 1종 또는 2종 이상을 혼합 사용할 수도 있다. 알킬카르보닐 클로라이드와 염기의 사용량에 있어서는, 상기 화학식 1a로 표시되는 화합물 1 몰을 기준으로 각각 1 ∼ 4 몰비 범위로 사용될 수 있고, 바람직하기로는 1 ∼ 2 몰비 범위로 사용될 수 있다.  The alkylcarbonylation process may be carried out under basic conditions with an alkylcarbonyl chloride. The alkylcarbonyl chloride may specifically include acetyl chloride, propionyl chloride, butyryl chloride, and the like. The base may be an organic base containing triethylamine, aliphatic amines such as diisopropylethylamine, aromatic amines such as dimethyl aniline, pyridine, etc., or an alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate and the like An inorganic base can be used. These bases may be used alone or in combination of two or more. The amount of the alkylcarbonyl chloride and the base to be used may be 1 to 4 molar ratio, preferably 1 to 2 molar ratio, based on 1 mol of the compound represented by the formula (1a).

상기 알킬카르보닐화 반응온도는 0℃ 내지 40℃ 범위에서 가능하며, 상온을 유지하는 것이 보다 바람직하다. 반응용매로는 당 분야에서 사용되어 온 통상의 유기용매는 모두 사용될 수 있으며 이의 선택에 특별한 제한을 두지 않는다. 반응용매를 구체적으로 예시하면 다이클로로메탄, 클로로포름, 1,2-다이클로로에탄, 다이에틸 에테르, 테트라하이드로퓨란, 에틸 아세테이트 등이 포함될 수 있다. 반응이 종료된 후에는 유기용매로 희석하여 물로 세척하고 얻어진 유기층을 건조, 농축하고 칼럼크로마토그래피로 정제할 수 있다.
The alkylcarbonylation reaction may be carried out at a temperature ranging from 0 ° C to 40 ° C, more preferably at a normal temperature. As the reaction solvent, any conventional organic solvent which has been used in the art can be used and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent include dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, ethyl acetate and the like. After completion of the reaction, the reaction mixture is diluted with an organic solvent, washed with water, and the obtained organic layer is dried, concentrated and purified by column chromatography.

한편, 상기 반응식 1 내지 3에 따른 제조방법에서 출발물질로 사용된 상기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시벤조에이트 화합물은 하기 반응식 4에 나타난 바와 같이 4 단계 제조과정을 걸쳐 합성될 수 있다.In the meantime, the 3-oxo-1-cycloalkenyl-3-alkoxybenzoate compound represented by the above formula (2) used as a starting material in the production method according to the above Reaction Schemes 1 to 3 can be prepared in four steps Can be synthesized throughout the process.

ⅰ단계) 하기 화학식 5로 표시되는 치환된 메틸 하이드록시벤조에이트를 Br-R4-Br로 표시되는 다이브로모알칸 시약과 반응시켜, 하기 화학식 6으로 표시되는 치환된 메틸 브로모알콕시 벤조에이트를 제조하는 과정;Step i) Substituted methylhydroxybenzoate represented by the following formula (5) is reacted with a dibromoalkane reagent represented by Br-R 4 -Br to prepare a substituted methyl bromoalkoxybenzoate represented by the following formula Process;

ⅱ단계) 하기 화학식 6으로 표시되는 화합물을 Z-H로 표시되는 아졸시약과 반응시켜, 하기 화학식 7로 표시되는 화합물을 제조하는 과정;(Ii) a step of reacting a compound represented by the following formula (6) with an azole reagent represented by Z-H to prepare a compound represented by the following formula (7);

ⅲ단계) 하기 화학식 7로 표시되는 화합물을 가수분해 반응시켜, 하기 화학식 8로 표시되는 벤조산 화합물을 제조하는 과정; 및(Iii) a step of hydrolyzing a compound represented by the formula (7) to prepare a benzoic acid compound represented by the following formula (8); And

ⅳ 단계) 하기 화학식 8로 표시되는 화합물을 하기 화학식 9로 표시되는 사이클로알칸 다이온 시약과 반응시켜, 하기 화학식 2로 표시되는 화합물을 제조하는 과정.(Iv) a step of reacting a compound represented by the following formula (8) with a cycloalkanedione reagent represented by the following formula (9) to prepare a compound represented by the following formula (2).

[반응식 4][Reaction Scheme 4]

Figure pat00034
Figure pat00034

(상기 반응식 4에서 R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같다)
(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in the above formula (1)

상기 반응식 4에 따른 제조방법을 보다 구체적으로 설명하면 하기와 같다.The production method according to Reaction Scheme 4 will be described in detail as follows.

ⅰ)단계 과정은 Br-R4-Br로 표시되는 다이브로모알칸 시약을 사용하여 진행되며, 염기 존재 하에서 통상의 유기용매를 사용하여 진행될 수 있다. 반응온도는 상온 내지 사용된 유기용매의 환류온도 범위이며, 구체적으로는 20℃ 내지 120℃이고, 바람직하기로는 50℃ 내지 80℃ 온도 범위를 유지하는 것이다.I) The step is carried out using a dibromoalkane reagent represented by Br-R 4 -Br, which may be carried out using a conventional organic solvent in the presence of a base. The reaction temperature is in the range of from room temperature to the reflux temperature of the organic solvent used, specifically, from 20 캜 to 120 캜, preferably from 50 캜 to 80 캜.

ⅱ) 단계 과정은 Z-H로 표시되는 아졸시약을 사용하여 진행되며, 염기 및 테트라부틸암모늄 브로마이드(TBAB) 촉매 존재 하에서 통상의 유기용매를 사용하여 진행될 수 있다. 반응온도는 상온 내지 사용된 유기용매의 환류온도 범위이며, 구체적으로는 20℃ 내지 120℃이고, 바람직하기로는 70℃ 내지 90℃ 온도 범위를 유지하는 것이다.Step ii) is carried out using an azole reagent represented by Z-H, and may be carried out using a conventional organic solvent in the presence of a base and a tetrabutylammonium bromide (TBAB) catalyst. The reaction temperature is in the range of from room temperature to the reflux temperature of the organic solvent used, specifically, from 20 to 120 ° C, preferably from 70 to 90 ° C.

ⅲ) 단계 과정은 에스터 그룹을 가수분해하여 카르복시산 그룹으로 전환한다. 상기 가수분해는 산 또는 염기를 사용하여 진행될 수 있다. 본 발명의 실시예에서는 주로 수산화나트륨을 포함하는 알칼리금속 수산화물을 사용한 알칼리 가수분해 조건에서 진행하였다.Iii) The step process converts the ester group to a carboxylic acid group by hydrolysis. The hydrolysis may be carried out using an acid or base. In the examples of the present invention, alkali hydrolysis using alkali metal hydroxide containing sodium hydroxide was mainly carried out.

ⅳ) 단계 과정은 사이클로알칸 다이온 시약을 사용하여, 염기 및 통상의 유기용매를 사용하는 조건에서 진행될 수 있다. 반응온도는 상온 내지 사용된 유기용매의 환류온도 범위이며, 구체적으로는 20℃ 내지 80℃이고, 바람직하기로는 상온 주변의 온도를 유지하는 것이다.Step iv) can be carried out using a cycloalkanedione reagent, a base and a conventional organic solvent. The reaction temperature is in the range of from room temperature to the reflux temperature of the organic solvent used, specifically, from 20 to 80 ° C, and preferably the temperature is maintained around room temperature.

본 발명의 제조방법에서 사용되는 통상의 염기는 유기염기 또는 무기염기가 포함될 수 있다. 상기 유기염기로는 트리(C1∼C6알킬)아민, 피리딘, 및 다이메틸 아닐린 등으로 이루어진 군으로부터 선택된 1종 이상이 사용될 수 있다. 상기 유기염기는 구체적으로 트리메틸아민, 트리에틸아민, 다이에틸이소프로필아민, 다이이소프로필에틸아민 등이 포함될 수 있다. 상기 무기염기로는 알칼리금속 또는 알칼리토금속의 수산화물, 수소화물, 카보네이트, 및 C1∼C6알콕사이드 등으로 이루어진 군으로부터 선택된 1종 이상이 사용될 수 있다. 상기 무기염기는 구체적으로 수산화리튬, 수산화나트륨, 수산화칼슘, 수소화나트륨, 수소화칼륨, 나트륨 메톡사이드, 칼륨 메톡사이드 등이 포함될 수 있다. 상기한 염기는 반응물질 1 몰을 기준으로 1 내지 3 몰비, 바람직하기로는 1 내지 2 몰비 범위로 사용할 수 있다.Conventional bases used in the production method of the present invention may include organic bases or inorganic bases. As the organic base, at least one selected from the group consisting of tri (C 1 -C 6 alkyl) amine, pyridine, and dimethyl aniline can be used. The organic base may specifically include trimethylamine, triethylamine, diethylisopropylamine, diisopropylethylamine, and the like. As the inorganic base, at least one selected from the group consisting of hydroxides of alkali metals or alkaline earth metals, hydrides, carbonates, and C 1 to C 6 alkoxides can be used. The inorganic base may specifically include lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium hydride, potassium hydride, sodium methoxide, potassium methoxide and the like. The above-mentioned base may be used in an amount of 1 to 3 mol, preferably 1 to 2 mol, based on 1 mol of the reactant.

또한, 본 발명의 제조방법에서 사용되는 통상의 유기용매로는 반응에 참여하지 않는 용매라면 모두 사용이 가능하다. 이러한 용매로는 예를 들면 다이에틸 에테르, 테트라히드로푸란(THF), 다이옥산, 다이메톡시에탄과 같은 에테르류; 다이클로로메탄, 1,2-다이클로로에탄, 클로로포름, 사염화탄소, 클로로벤젠과 같은 할로겐화 탄화수소류; 벤젠, 톨루엔, 크실렌과 같은 방향족 탄화수소류; 노말헥산, 사이클로헥산, 헵탄 등의 지방족 탄화수소류; 아세토나이트릴, 프로피오나이트릴과 같은 나이트류; 아세톤과 같은 케톤류; 에틸 아세테이트와 같은 아세테이트류; 다이메틸포름아마이드(DMF)와 같은 아마이드류; 등으로 이루어진 군으로부터 선택된 1종 또는 2종 이성을 적절하게 선택하여 사용할 수 있다.
As the conventional organic solvent used in the production method of the present invention, any solvent which does not participate in the reaction can be used. Such solvents include, for example, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane; Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, and chlorobenzene; Aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic hydrocarbons such as normal hexane, cyclohexane, and heptane; Nitrites such as acetonitrile and propionitrile; Ketones such as acetone; Acetates such as ethyl acetate; Amides such as dimethylformamide (DMF); And the like can be appropriately selected and used.

이상에서 설명한 바와 같은 본 발명은 하기의 실시예에 의거하여 더욱 상세히 설명하겠으나, 본 발명이 이에 한정된 것은 아니다.The present invention will now be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[실시예]
[Example]

본 실시예를 통해 합성된 상기 화학식 1로 표시되는 화합물을 구체적으로 예시하면 하기 표 1과 같다. 통상의 당업자라면 하기 표 1에 예시된 화합물은 본 실시예로 구체화되어 있는 합성법을 이용하거나 응용하여 쉽게 합성할 수 있다.
The compounds represented by the above formula (1) synthesized through this embodiment are specifically exemplified in Table 1 below. Those skilled in the art can easily synthesize the compounds exemplified in the following Table 1 by using or applying the synthesis method embodied in this embodiment.

Figure pat00035
Figure pat00035
Com. NoCom. No R1 R 1 R2 R 2 R3 R 3 R4 R 4 nn XX YY ZZ 1One OHOH HH HH CH2 CH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 22 OHOH HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 33 OHOH HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-1Z-1 44 OHOH HH HH (CH2)4 (CH 2 ) 4 00 ClCl SO2MeSO 2 Me Z-1Z-1 55 OHOH HH HH (CH2)5 (CH 2) 5 00 ClCl SO2MeSO 2 Me Z-1Z-1 66 OHOH HH HH CH2 CH 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 77 OHOH HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 88 OHOH HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-2Z-2 99 OHOH HH HH (CH2)4 (CH 2 ) 4 00 ClCl SO2MeSO 2 Me Z-2Z-2 1010 OHOH HH HH (CH2)5 (CH 2) 5 00 ClCl SO2MeSO 2 Me Z-2Z-2 1111 OHOH HH HH CH2 CH 2 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1212 OHOH HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1313 OHOH HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1414 OHOH HH HH (CH2)4 (CH 2 ) 4 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1515 OHOH HH HH (CH2)5 (CH 2) 5 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1616 OHOH HH HH CH2 CH 2 00 ClCl SO2MeSO 2 Me Z-3-2Z-3-2 1717 OHOH HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-3-2Z-3-2 1818 OHOH MeMe HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 1919 OHOH MeMe HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 2020 OHOH MeMe HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 2121 OHOH HH HH CH2 CH 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 2222 OHOH HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 2323 OHOH HH HH (CH2)3 (CH 2 ) 3 22 ClCl SO2MeSO 2 Me Z-1Z-1 2424 OHOH HH HH CH2 CH 2 22 ClCl SO2MeSO 2 Me Z-2Z-2 2525 OHOH HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-2Z-2 2626 OHOH HH HH (CH2)3 (CH 2 ) 3 22 ClCl SO2MeSO 2 Me Z-2Z-2 2727 OHOH HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 2828 OHOH HH HH (CH2)3 (CH 2 ) 3 22 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 2929 OHOH HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-3-2Z-3-2 3030 OHOH HH HH CH2 CH 2 22 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 3131 OHOH HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-4Z-4 3232 OHOH HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-3-3Z-3-3 3333 OHOH HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-3-4Z-3-4 3434 OHOH HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-3-3Z-3-3 3535 OHOH HH HH (CH2)2OCH2 (CH 2 ) 2 OCH 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 3636 OHOH HH HH (CH2)4 (CH 2 ) 4 22 ClCl SO2MeSO 2 Me Z-1Z-1 3737 OHOH HH HH (CH2)4 (CH 2 ) 4 22 ClCl SO2MeSO 2 Me Z-2Z-2 3838 OHOH HH HH (CH2)2OCH2 (CH 2 ) 2 OCH 2 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 3939 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 4040 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 4141 OHOH HH HH (CH2)2 (CH 2) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 4242 OHOH HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 4343 OHOH HH HH (CH2)2 (CH 2) 2 22 MeMe SO2MeSO 2 Me Z-1Z-1 4444 OHOH HH HH (CH2)2 (CH 2) 2 00 MeMe NO2 NO 2 Z-1Z-1 4545 OHOH HH HH CH2CH=CHCH2
(cis)CH 2 CH = CHCH 2
(cis) 00 ClCl SO2MeSO 2 Me Z-1Z-1 4646 OHOH HH HH (CH2)2 (CH 2) 2 22 MeMe NO2 NO 2 Z-1Z-1 4747 OHOH HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 MeMe SO2MeSO 2 Me Z-1Z-1 4848 OHOH HH HH CH2CCCH2 CH 2 CCCH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 4949 OHOH HH HH CH2OCH2 CH 2 OCH 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 5050 OHOH HH HH CH2OCH2 CH 2 OCH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5151 OHOH HH HH CH2CHFCH 2 CHF 22 ClCl SO2MeSO 2 Me Z-1Z-1 5252 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5353 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5454 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5555 OC(O)t-BuOC (O) t- Bu HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5656 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 5757 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 5858 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 5959 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6060 OC(O)t-BuOC (O) t- Bu HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6161 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6262 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6363 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6464 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6565 OC(O)t-BuOC (O) t- Bu HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6666 OC(O)EtOC (O) Et HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6767 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 6868 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 6969 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 7070 OC(O)t-BuOC (O) t- Bu HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 7171 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 7272 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7373 OC(O)c-PrOC (O) c -Pr HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7474 OC(O)t-BuOC (O) t- Bu HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7575 OC(O)i-PrOC (O) i -Pr HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7676 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2) 2 22 MeMe SO2MeSO 2 Me Z-1Z-1 7777 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2) 2 00 MeMe NO2 NO 2 Z-1Z-1 7878 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2
(cis)CH 2 CH = CHCH 2
(cis) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7979 OC(O)i-PrOC (O) i -Pr HH HH CH2CH=CHCH2 (cis)CH 2 CH = CHCH 2 (cis) 00 ClCl SO2MeSO 2 Me Z-1Z-1 8080 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 MeMe SO2MeSO 2 Me Z-1Z-1 8181 OC(O)MeOC (O) Me HH HH CH2CCCH2 CH 2 CCCH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 8282 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2) 2 22 MeMe NO2 NO 2 Z-1Z-1 8383 OC(O)MeOC (O) Me HH HH CH2CHFCH 2 CHF 22 ClCl SO2MeSO 2 Me Z-1Z-1 8484 OC(O)t-BuOC (O) t- Bu HH HH CH2CHFCH 2 CHF 22 ClCl SO2MeSO 2 Me Z-1Z-1 8585 ClCl HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 8686 ClCl HH HH (CH2)4 (CH 2 ) 4 00 ClCl SO2MeSO 2 Me Z-1Z-1 8787 ClCl HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-3-4Z-3-4 8888 ClCl HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-3-3Z-3-3 8989 ClCl HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-3-2Z-3-2 9090 ClCl HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 9191 ClCl HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 9292 ClCl HH HH (CH2)2 (CH 2) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 9393 ClCl HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-1Z-1 9494 ClCl HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 9595 ClCl HH HH (CH2)2 (CH 2) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 9696 ClCl HH HH (CH2)2 (CH 2) 2 22 MeMe SO2MeSO 2 Me Z-1Z-1 9797 ClCl HH HH (CH2)2 (CH 2) 2 00 MeMe NO2 NO 2 Z-1Z-1 9898 ClCl HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 MeMe SO2MeSO 2 Me Z-1Z-1 9999 ClCl HH HH CH2CHFCH 2 CHF 22 ClCl SO2MeSO 2 Me Z-1Z-1 100100 OC(O)t-BuOC (O) t- Bu HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 101101 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 102102 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 103103 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 0　0 ClCl SO2MeSO 2 Me Z-2Z-2 104104 OC(O)i-PrOC (O) i -Pr HH HH CH2CCCH2 CH 2 CCCH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 105105 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2
(cis)CH 2 CH = CHCH 2
(cis) 00 MeMe NO2 NO 2 Z-1Z-1 106106 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 MeMe NO2 NO 2 Z-1Z-1 107107 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2
(cis)CH 2 CH = CHCH 2
(cis) 00 MeMe SO2MeSO 2 Me Z-1Z-1 108108 OHOH HH HH CH2CH=CHCH2
(cis)CH 2 CH = CHCH 2
(cis) 00 MeMe NO2 NO 2 Z-1Z-1 109109 ClCl HH HH CH2CH=CHCH2
(cis)CH 2 CH = CHCH 2
(cis) 00 MeMe NO2 NO 2 Z-1Z-1 110110 OHOH HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 MeMe NO2 NO 2 Z-1Z-1 111111 ClCl HH HH CH2CH=CHCH2
(trans)CH 2 CH = CHCH 2
(trans) 00 MeMe NO2 NO 2 Z-1Z-1 112112 OHOH HH HH CH2OCH2 CH 2 OCH 2 00 ClCl NO2 NO 2 Z-1Z-1 113113 OHOH HH HH CH2OCH2 CH 2 OCH 2 00 MeMe NO2 NO 2 Z-1Z-1 114114 OHOH HH HH CH2CH=CHCH2
(cis)CH 2 CH = CHCH 2
(cis) 00 MeMe SO2MeSO 2 Me Z-1Z-1 115115 ClCl HH HH CH2CH=CHCH2
(cis)CH 2 CH = CHCH 2
(cis) 00 MeMe SO2MeSO 2 Me Z-1Z-1 116116 FF HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 117117 FF HH HH (CH2)2 (CH 2) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 118118 FF HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-1Z-1 119119 BrBr HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-1Z-1 120120 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 121121 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 122122 ClCl HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 123123 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 124124 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 125125 ClCl HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 126126 OHOH HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 127127 OC(O)MeOC (O) Me HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 128128 ClCl HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 129129 OHOH HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 130130 OC(O)MeOC (O) Me HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 131131 OHOH HH HH CH2SCH2 CH 2 SCH 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 132132 OHOH HH HH (CH2)2S(CH2)2 (CH 2 ) 2 S (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 133133 ClCl HH HH CH2CHFCH 2 CHF 00 MeMe SO2MeSO 2 Me Z-2Z-2 134134 OHOH HH HH CH2CHFCH 2 CHF 00 MeMe SO2MeSO 2 Me Z-1Z-1 135135 ClCl HH HH CH2CHFCH 2 CHF 00 MeMe SO2MeSO 2 Me Z-1Z-1 136136 OC(O)MeOC (O) Me HH HH CH2CHFCH 2 CHF 00 MeMe SO2MeSO 2 Me Z-1Z-1

상기 표 1에서 구체화된 화합물들의 구조분석 결과는 하기 표 2와 같다.The results of structural analysis of the compounds embodied in Table 1 are shown in Table 2 below.

Com.
No.Com.
No. NMRNMR 1One 1H NMR (300 MHz, CDCl3) δ 8.03 (d, J = 8.2 Hz, 1H), 7.74 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 6.39 (s, 2H), 3.26 (s, 3H), 3.01 (t, J = 7.0 Hz, 2H), 2.42-2.34 (m, 2H), 2.04-2.00 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.03 (d, J = 8.2 Hz, 1H), 7.74 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 6.39 (s, 2H), 3.26 (s, 3H), 3.01 (t, J = 7.0 Hz, 2H), 2.42-2.34 (m, 2H), 2.04-2.00 22 1H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz, 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81- 2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz 2H), 2.68-2.40 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H), 4.68 (t, J = 4.8 Hz, 2H) 2H) 33 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.70 (s, 2H), 7.64 (d, J = 8.2 Hz, 1H), 4.76 (t, J = 7.0 Hz, 2H),4.33 (t, J = 6.0 Hz, 2H), 3.65-3.63 (m, 2H), 3.37 (s, 3H), 2.64-2.56 (m, 2H), 2.43- 2.40 (m, 2H), 2.06-1.85 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.70 (s, 2H), 7.64 (d, J = 8.2 Hz, 1H), 4.76 (t, J = 7.0 Hz , 2H), 4.33 (t, J = 6.0 Hz, 2H), 3.65-3.63 (m, 2H), 3.37 (s, 3H), 2.64-2.56 (m, 2H), 2.43- 2.40 (m, 2H), 2.06-1.85 (m, 2H) 44 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 7.5 Hz, 1H), 7.63 (s, 2H), 7.09 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 6.8 Hz, 2H), 4.30 (t, J = 6.2 Hz, 2H), 3.27 (s, 3H), 2.83 (t, 2H), 2.47 (t, 2H), 2.24 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 1.94-1.90 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.95 (d, J = 7.5 Hz, 1H), 7.63 (s, 2H), 7.09 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 6.8 Hz , 2H), 4.30 (t, J = 6.2 Hz, 2H), 3.27 (s, 3H), 2.83 (t, 2H), 2.47 (t, 2H), 2.24 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 1.94-1.90 (m, 2H) 55 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.58 (s, 2H), 7.05 (d, J = 8.1 Hz, 1H), 4.49 (t, J = 6.9 Hz, 2H), 4.22 (t, J = 6.4 Hz, 2H), 3.24 (s, 3H), 2.81 (t, J = 6.0 Hz, 2H), 2.44 (t, J = 6.0 Hz, 2H), 2.11-2.02 (m, 4H), 1.94- 1.89 (m, 2H), 1.59-1.49 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.58 (s, 2H), 7.05 (d, J = 8.1 Hz, 1H), 4.49 (t, J = 6.9 Hz , 2H), 4.22 (t, J = 6.4 Hz, 2H), 3.24 (s, 3H), 2.81 (t, J = 6.0 Hz, 2H), 2.44 (t, J = 6.0 Hz, 2H), 2.11-2.02 (m, 4H), 1.94 - 1.89 (m, 2H), 1.59-1. 49 (m, 2H) 66 1H NMR (300 MHz, CDCl3) δ 8.13 (s, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 8.2 Hz, 1H), 7.82 (s, 1H), 6.37 (s, 2H), 3.19 (s, 3H), 2.43-2.34 (m, 4H), 1.96-1.89 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.13 (s, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 8.2 Hz, 1H), 7.82 (s, 1H), 6.37 (s, 2H), 3.19 (s, 3H), 2.43-2.34 (m, 4H), 1.96-1.89 77 1H NMR (500 MHz, CDCl3) δ 8.17 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72 (s, 1H), 7.19 (d, J = 8.0 Hz, 1H), 5.00 (t, J = 4.7 Hz, 2H), 4.64 (t, J = 4.7 Hz, 2H), 3.20 (s, 3H), 2.62-2.60 (m, 2H), 2.55-2.53 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H) 1 H NMR (500 MHz, CDCl 3) δ 8.17 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72 (s, 1H), 7.19 (d, J = 8.0 Hz, 1H), 5.00 (t, J = 4.7 Hz, 2H), 4.64 (t, J = 4.7 Hz, 2H), 3.20 (s, 3H), 2.62-2.60 (m, 2H), 2.55-2.53 quin, J = 6.5 Hz, 2H) 88 1H NMR (300 MHz, Acetone-d 6) δ 7.99 (s, 1H), 7.81 (d, J = 8.2 Hz, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.60 (s, 1H), 4.66 (t, J = 7.2 Hz, 2H), 4.22 (t, J = 6.0 Hz, 2H), 3.51-3.49 (m, 2H), 3.22 (s, 3H), 2.45 (t, J = 6.7 Hz, 2H), 2.23 (t, J = 6.7 Hz, 2H), 1.81-1.71 (m, 2H) 1 H NMR (300 MHz, Acetone- d 6) δ 7.99 (s, 1H), 7.81 (d, J = 8.2 Hz, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.60 (s, 1H) , 4.66 (t, J = 7.2 Hz, 2H), 4.22 (t, J = 6.0 Hz, 2H), 3.51-3.49 (m, 2H), 3.22 (s, 3H), 2.45 (t, J = 6.7 Hz, 2H), 2.23 (t, J = 6.7 Hz, 2H), 1.81 - 1.71 (m, 2H) 99 1H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 8.1 Hz, 1H), 7.76 (s, 1H), 7.64 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 4.54 (t, J = 7.5 Hz, 2H), 4.30 (t, J = 6.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 7.5 Hz, 2H), 2.22 (t, J = 6.5 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.97-1.93 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.96 (d, J = 8.1 Hz, 1H), 7.76 (s, 1H), 7.64 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 4.54 (t, J = 7.5 Hz, 2H), 4.30 (t, J = 6.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 7.5 Hz 2H), 2.22 (t, J = 6.5 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.97-1.93 1010 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.50-4.42 (m, 2H), 4.22 (t, J = 6.0 Hz, 2H), 3.23 (s, 3H), 2.60 (t, J = 6.6 Hz, 2H), 2.36 (t, J = 6.3 Hz, 2H), 2.11-1.87 (m, 6H), 1.57-1.49 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.50 -4.42 (m, 2H), 4.22 (t, J = 6.0 Hz, 2H), 3.23 (s, 3H), 2.60 (t, J = 6.6 Hz, 2H), 2.36 (t, J = 6.3 Hz, 2H) , 2.11-1.87 (m, 6H), 1.57-1. 49 (m, 2H) 1111 1H NMR (300 MHz, CDCl3) δ 8.38 (s, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.96 (s, 1H), 7.88 (d, J = 8.2 Hz, 1H), 6.37 (s, 2H), 3.19 (s, 3H), 2.43-2.34 (m, 4H), 1.96 -1.89 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.38 (s, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.96 (s, 1H), 7.88 (d, J = 8.2 Hz, 1H), 6.37 (s, 2H), 3.19 (s, 3H), 2.43-2.34 (m, 4H), 1.96-1.89 1212 1H NMR (300 MHz, CDCl3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04 (t, J = 6.5 Hz, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 t, J = 6.5 Hz, 2H) 1313 1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.98 (s, 1H), 7.32 (d, J = 8.1 Hz, 1H), 4.51 (t, J = 6.6 Hz, 2H), 4.33 (t, J = 5.5 Hz, 2H), 3.72- 3.70 (m, 2H), 3.26 (s, 3H), 2.98- 2.40 (m, 4H), 2.06- 1.93 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.27 (s, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.98 (s, 1H), 7.32 (d, J = 8.1 Hz, 1H), 4.51 (t, J = 6.6 Hz, 2H), 4.33 (t, J = 5.5 Hz, 2H), 3.72- 3.70 (m, 2H), 3.26 (s, 3H), 2.98- 2.40 (m, 4H), 2.06- 1.93 (m, 2 H) 1414 1H NMR (500 MHz, CDCl3) δ 8.18 (s, 1H), 8.00 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 4.34-4.29 (m, 4H), 3.26 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.19 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.95-1.91 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 8.18 (s, 1H), 8.00 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 4.34 J = 6.0 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.19 (t, J = 7.0 Hz, 2H) , 2.10 (t, J = 6.5 Hz, 2H), 1.95-1.91 (m, 2H) 1515 1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.28 (t, J = 6.9 Hz, 2H), 3.58-3.53 (m, 2H), 3.24 (s, 3H), 2.64 (t, J = 6.6 Hz, 2H), 2.32 (t, J = 6.6 Hz, 2H), 2.10-1.93 (m, 6H), 1.60-1.45 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.28 (t, J = 6.9 Hz, 2H), 3.58-3.53 (m, 2H), 3.24 (s, 3H), 2.64 (t, J = 6.6 Hz, 2H), 2.32 (t, J = 6.6 Hz, 2H) , 2.10-1.93 (m, 6H), 1.60-1. 45 (m, 2H) 1616 1H NMR (300 MHz, CDCl3) δ 8.59 (s, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.23 (d, J = 8.1 Hz, 1H), 6.17 (s, 2H), 3.19 (s, 3H), 2.85 (t, J = 6.3 Hz, 2H), 2.46 (t, J = 6.3 Hz, 2H), 2.10 (quin, J = 6.5 Hz, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.59 (s, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.23 (d, J = 8.1 Hz, 1H), 6.17 (s, 2H), 3.19 (s, 3H), 2.85 ( t, J = 6.3 Hz, 2H), 2.46 (t, J = 6.3 Hz, 2H), 2.10 (quin, J = 6.5 Hz, 2H) 1717 1H NMR (500 MHz, CDCl3) δ 8.40 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.14 (d, J = 8.0 Hz, 1H), 4.74 (t, J = 4.8 Hz, 2H), 4.67 (t, J = 4.8 Hz, 2H), 3.15 (s, 3H), 2.86-2.84 (m, 2H), 2.47-2.45 (m, 2H), 2.10 (quin, J = 6.5 Hz, 2H) 1 H NMR (500 MHz, CDCl 3) δ 8.40 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.14 (d, J = 8.0 Hz, 1H), 4.74 (t, J = 4.8 Hz 2H), 2.47-2.45 (m, 2H), 2.10 (quin, J = 6.5 Hz, 2H), 4.67 (t, J = 4.8 Hz, 2H) 2H) 1818 1H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz, 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81- 2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07-1.98 (m, 1H), 1.95 (d, J = 8.0 Hz, 3H) 1 H NMR (500 MHz, CDCl 3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz 2H), 2.68-2.40 (m, 2H), 2.07-1.98 (m, 1H), 4.68 (t, J = 4.8 Hz, 2H) 1.95 (d, J = 8.0 Hz, 3 H) 1919 1H NMR (500 MHz, CDCl3) δ 8.17 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72 (s, 1H), 7.19 (d, J = 8.0 Hz, 1H), 5.00 (t, J = 4.7 Hz, 2H), 4.64 (t, J = 4.7 Hz, 2H), 3.20 (s, 3H), 2.62-2.60 (m, 2H), 2.55-2.53 (m, 2H), 2.07-2.01 (m, 1H), 1.99 (d, J = 8.0 Hz, 3H) 1 H NMR (500 MHz, CDCl 3) δ 8.17 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72 (s, 1H), 7.19 (d, J = 8.0 Hz, 1H), 5.00 (t, J = 4.7 Hz, 2H), 4.64 (t, J = 4.7 Hz, 2H), 3.20 (s, 3H), 2.62-2.60 (m, 2H), 2.55-2.53 (m, 2H), 2.07- 2.01 (m, 1H), 1.99 (d, J = 8.0 Hz, 3H) 2020 1H NMR (300 MHz, CDCl3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04-2.01 (m, 1H), 2.00 (d, J = 8.0 Hz, 3H) 1 H NMR (300 MHz, CDCl 3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04- 2.01 (m, 1H), 2.00 (d, J = 8.0 Hz, 3H) 2121 1H NMR (500 MHz, CDCl3) δ 8.05 (d, J = 7.9 Hz, 1H), 7.75 (s, 2H), 7.79 (d, J = 8.2 Hz, 1H), 6.42 (s, 2H), 3.38-3.25 (m, 2H), 3.21 (s, 3H), 2.35-2.17 (m, 4H), 1.69-1.64 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 8.05 (d, J = 7.9 Hz, 1H), 7.75 (s, 2H), 7.79 (d, J = 8.2 Hz, 1H), 6.42 (s, 2H), 3.38 2H), 3.21 (s, 3H), 2.35-2.17 (m, 4H), 1.69-1.64 (m, 2H) 2222 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 8.5 Hz, 1H), 7.63 (s, 2H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42-3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 8.5 Hz, 1H), 7.63 (s, 2H), 4.78 (t, J = 7.1 Hz , 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42-3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 2323 1H NMR (300 MHz, CDCl3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 8.8 Hz, 1H), 7.63 (s, 2H), 4.75 (t, J = 7.1 Hz, 2H), 4.34 (t, J = 6.0 Hz, 2H), 3.43 (t, J = 4.2 Hz, 1H), 3.31-3.28 (m, 2H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64- 2.55 (m, 3H), 1.99-1.84 (m, 1H), 1.67-1.62 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 8.8 Hz, 1H), 7.63 (s, 2H), 4.75 (t, J = 7.1 Hz , 2H), 4.34 (t, J = 6.0 Hz, 2H), 3.43 (t, J = 4.2 Hz, 1H), 3.31-3.28 (m, 2H), 3.28 (s, 3H), 3.16 (t, J = 1H), 1.67-1.62 (m, 2H), 2.64-2.55 (m, 3H) 2424 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.77 (t, J = 7.1 Hz, 2H), 4.30 (t, J = 6.5 Hz, 2H), 3.45-3.28 (m, 3H), 3.28 (s, 3H), 3.10 (t, J = 6.0 Hz, 1H), 2.64-2.50 (m, 1H), 1.92-1.82 (m, 1H), 1.69-1.63 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.77 (t, J = 7.1 Hz, 2H), 4.30 (t, J = 6.5 Hz, 2H), 3.45-3.28 (m, 3H), 3.28 (s, 3H), 3.10 (t, J = 6.0 Hz, 1H) , 2.64-2.50 (m, 1 H), 1.92-1.82 (m, 1 H), 1.69-1.63 (m, 2 H) 2525 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.77 (t, J = 7.1 Hz, 2H), 4.30 (t, J = 6.5 Hz, 2H), 3.45- 3.28 (m, 3H), 3.28 (s, 3H), 3.10 (t, J = 6.0 Hz, 1H), 2.64-2.50 (m, 1H), 1.92-1.82 (m, 1H), 1.69-1.63 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.77 (t, J = 7.1 Hz, 2H), 4.30 (t, J = 6.5 Hz, 2H), 3.45- 3.28 (m, 3H), 3.28 (s, 3H), 3.10 (t, J = 6.0 Hz, 1H) , 2.64-2.50 (m, 1 H), 1.92-1.82 (m, 1 H), 1.69-1.63 (m, 2 H) 2626 1H NMR (300 MHz, CDCl3) δ 7.98 (d, J = 8.2 Hz, 1H), 7.76 (s, 1H), 7.72 (d, J = 9.8 Hz, 1H), 7.72 (s, 1H), 4.71 (t, J = 7.0 Hz, 2H), 4.34 (t, J = 5.8 Hz, 2H), 3.32- 3.31 (m, 1H), 3.25 (s, 3H), 2.95- 2.78 (m, 2H), 2.59-2.48 (m, 2H), 2.30-2.12 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.98 (d, J = 8.2 Hz, 1H), 7.76 (s, 1H), 7.72 (d, J = 9.8 Hz, 1H), 7.72 (s, 1H), 4.71 (t, J = 7.0 Hz, 2H), 4.34 (t, J = 5.8 Hz, 2H), 3.32- 3.31 (m, 1H), 3.25 (s, 3H), 2.95- 2.78 (m, 2H), 2.59- 2.48 (m, 2 H), 2.30 - 2.12 (m, 2 H) 2727 1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42- 3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42- 3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H) , 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 2828 1H NMR (300 MHz, CDCl3) δ 8.34 (s, 1H), 8.02 (s, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 8.2 Hz, 1H), 4.52 (t, J = 7.0 Hz, 2H), 4.39-4.29 (m, 2H), 3.43-3.41 (m, 1H), 3.24 (s, 3H), 2.90-2.81 (m, 2H), 2.58-2.48 (m, 3H), 2.13-1.84 (m, 4H) 1 H NMR (300 MHz, CDCl 3) δ 8.34 (s, 1H), 8.02 (s, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 8.2 Hz, 1H), 4.52 (t, J = 7.0 Hz, 2H), 4.39-4.29 (m, 2H), 3.43-3.41 (m, 1H), 3.24 (s, 3H), 2.90-2.81 (m, 2H), 2.58-2.48 (m , ≪ / RTI > 3H), 2.13-1.84 (m, 4H) 2929 1H NMR (500 MHz, CDCl3) δ 8.40 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.17 (d, J = 8.0 Hz, 1H), 4.74 (t, J = 4.6 Hz, 2H), 4.67 (t, J = 4.6 Hz, 2H), 3.20 (t, J = 4.6 Hz, 1H), 3.14 (s, 3H), 2.92 (t, J = 5.5 Hz, 1H), 2.30-2.14 (m, 3H), 2.08-2.03 (m, 1H), 1.82-1.78 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 8.40 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.17 (d, J = 8.0 Hz, 1H), 4.74 (t, J = 4.6 Hz , 2H), 4.67 (t, J = 4.6 Hz, 2H), 3.20 (t, J = 4.6 Hz, 1H), 3.14 (s, 3H), 2.92 (t, J = 5.5 Hz, 1H), 2.30-2.14 (m, 3H), 2.08-2.03 (m, 1H), 1.82-1.78 (m, 2H) 3131 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.1 Hz, 1H), 7.59 (d, J = 6.4 Hz, 2H), 7.10 (d, J = 8.1 Hz, 1H), 6.31 (s, 1H), 4.64 (s, 4H), 3.13 (s, 3H), 2.83 (t, J = 6.0 Hz, 2H), 2.45 (t, J = 6.0 Hz, 2H), 2.10- 2.06 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.1 Hz, 1H), 7.59 (d, J = 6.4 Hz, 2H), 7.10 (d, J = 8.1 Hz, 1H), 6.31 (s , 1H), 4.64 (s, 4H), 3.13 (s, 3H), 2.83 (t, J = 6.0 Hz, 2H), 2.45 (t, J = 6.0 Hz, 2H), 2.10- 2.06 (m, 2H) 3232 1H NMR (500 MHz, CDCl3) δ 8.02 (s, 1H), 7.96 (d, J = 8.1Hz, 1H), 7.14 (d, J = 8.1Hz, 1H), 4.67-4.55 (m, 4H), 3.17 (s, 3H), 2.85 (t, J = 6.1Hz, 2H), 2.47 (t, J = 6.0Hz, 2H), 2.10 (t, J = 6.3Hz, 2H) 1 H NMR (500 MHz, CDCl 3) δ 8.02 (s, 1H), 7.96 (d, J = 8.1Hz, 1H), 7.14 (d, J = 8.1Hz, 1H), 4.67-4.55 (m, 4H) , 3.17 (s, 3H), 2.85 (t, J = 6.1Hz, 2H), 2.47 (t, J = 6.0Hz, 2H), 2.10 (t, J = 6.3Hz, 2H) 3535 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 9.6 Hz, 2H), 7.09 (d, J = 8.2 Hz, 1H), 5.85 (s, 2H), 4.38 (t, J = 4.2 Hz, 2H), 3.95 (t, J = 4.2 Hz, 2H), 3.25 (s, 3H), 2.82 (t, J = 6.2 Hz, 2H), 2.44 (t, J = 6.6 Hz, 2H), 2.07 (quin, J = 6.5 Hz, 2H). 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 9.6 Hz, 2H), 7.09 (d, J = 8.2 Hz, 1H), 5.85 (s , 2H), 4.38 (t, J = 4.2 Hz, 2H), 3.95 (t, J = 4.2 Hz, 2H), 3.25 (s, 3H), 2.82 (t, J = 6.2 Hz, 2H), 2.44 (t , J = 6.6 Hz, 2H), 2.07 (quin, J = 6.5 Hz, 2H). 3636 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.1 Hz, 1H), 7.75 (s, 2H), 7.11 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 7.2 Hz, 2H), 4.29 (t, J = 7.1 Hz, 2H), 3.27 (s, 3H), 3.19-3.17 (m 1H), 3.08-3.05 (m, 1H), 2.29-2.11 (m, 4H), 1.93-1.89 (m, 4H), 1.82-1.77 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.95 (d, J = 8.1 Hz, 1H), 7.75 (s, 2H), 7.11 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 7.2 Hz 2H), 4.29 (t, J = 7.1 Hz, 2H), 3.27 (s, 3H), 3.19-3.17 (mH), 3.08-3.05 -1.89 (m, 4 H), 1.82 - 1.77 (m, 2 H) 3838 1H NMR (300 MHz, CDCl3) δ 8.25 (s, 1H), 7.92 (s, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H), 5.58 (s, 2H), 4.34 (t, J = 4.1 Hz, 2H), 3.94 (t, J = 4.3 Hz, 2H), 3.18 (s, 3H), 2.75-2.73 (m, 2H), 2.37-2.35 (m, 2H), 2.00-1.98 (m, 2H). 1 H NMR (300 MHz, CDCl 3) δ 8.25 (s, 1H), 7.92 (s, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H), 5.58 (s, 2H), 4.34 (t, J = 4.1 Hz, 2H), 3.94 (t, J = 4.3 Hz, 2H), 3.18 (s, 3H), 2.75-2.73 m, 2 H), 2.00 - 1.98 (m, 2 H). 3939 1H NMR (500 MHz, CDCl3) δ 7.94 (d, J = 7.9 Hz, 1H), 7.61 (s, 2H), 7.07 (d, J = 7.9 Hz, 1H), 4.67 (t, J = 4.9 Hz, 2H), 4.36 (t, J = 4.0 Hz, 2H), 4.12 (t, J = 4.9 Hz, 2H), 3.87 (t, J = 4.0 Hz, 2H), 3.26 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.44 (t, J = 6.3 Hz,, 2H), 2.09-1.98 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.94 (d, J = 7.9 Hz, 1H), 7.61 (s, 2H), 7.07 (d, J = 7.9 Hz, 1H), 4.67 (t, J = 4.9 Hz , 2H), 4.36 (t, J = 4.0 Hz, 2H), 4.12 (t, J = 4.9 Hz, 2H), 3.87 (t, J = 4.0 Hz, 2H), 3.26 (s, 3H), 2.82 (t , J = 6.3 Hz, 2H) , 2.44 (t, J = 6.3 Hz ,, 2H), 2.09-1.98 (m, 2H) 4040 1H NMR (500 MHz, CDCl3) δ 7.97 (d, J = 8.1 Hz, 1H), 7.83 (s, 1H), 7.71 (s, 1H), 7.12 (d, J = 8.1 Hz, 1H), 4.65 (t, J = 4.9 Hz, 2H), 4.42 (t, J = 4.0 Hz, 2H), 3.97 (t, J = 4.9 Hz, 2H), 3.91 (t, J = 4.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.3 Hz, 2H), 2.47 (t, J = 6.4 Hz,, 2H), 2.12-2.09 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.97 (d, J = 8.1 Hz, 1H), 7.83 (s, 1H), 7.71 (s, 1H), 7.12 (d, J = 8.1 Hz, 1H), 4.65 (t, J = 4.9 Hz, 2H), 4.42 (t, J = 4.0 Hz, 2H), 3.97 (t, J = 4.9 Hz, 2H), 3.91 (t, J = 4.0 Hz, 2H), 3.25 (s J = 6.4 Hz, 2H), 2.12-2.09 (m, 2H), 2.85 (t, J = 4141 1H NMR (300 MHz, CDCl3) δ 7.83 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.97 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.80 (t, 2H), 2.43 (t, 2H), 2.06 (m, 2H), 2.06 (s, 3H) ; Mass : 419 1 H NMR (300 MHz, CDCl 3) δ 7.83 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.97 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.80 (t, 2H), 2.43 (t, 2H), 2.06 (m, 2H), 2.06 Mass: 419 4242 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.13-6.2 (m, 1H), 5.98-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.77 (d, J = 5.3 Hz, 1H), 3.25 (s, 3H), 2.75-2.88 (m, 2H), 2.38-2.52 (m, 2H), 2.00-2.14 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.13-6.2 (m, 1H), 5.98-6.11 (m, 1H ), 5.14 (d, J = 5.6 Hz, 2H), 4.77 (d, J = 5.3 Hz, 1H), 3.25 (s, 3H), 2.75-2.88 (m, 2H ), 2.38-2.52 (m, 2H), 2.00-2.14 (m, 2H) 4343 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.2 Hz), 7.68 (s, 2H), 7.02 (d, 1H, J = 8.2 Hz), 4.93 (t, 2H), 4.57 (t, 2H), 3.26 (s, 3H), 3.18 (t, 1H), 2.90 (t, 1H), 2.11-2.29 (m, 3H), 2.03 (m, 1H), 1.94 (s, 3H), 1.76 (m, 2H) ; Mass : 445 1 H NMR (300 MHz, CDCl 3) δ 7.86 (d, 1H, J = 8.2 Hz), 7.68 (s, 2H), 7.02 (d, 1H, J = 8.2 Hz), 4.93 (t, 2H), 4.57 (t, 2H), 3.26 (s, 3H), 3.18 (t, IH), 2.90 (t, IH), 2.11-2.29 (m, 1.76 (m, 2H); Mass: 445 4444 1H NMR (300 MHz, CDCl3) δ 7.73 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.92 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.56 (t, 2H), 2.82 (t, 2H), 2.44 (t, 2H), 2.08 (m, 2H), 1.92 (s, 3H) ; Mass : 386 1 H NMR (300 MHz, CDCl 3) δ 7.73 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.92 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.56 (t, 2H), 2.82 (t, 2H), 2.44 (t, 2H), 2.08 (m, 2H), 1.92 (s, 3H); Mass: 386 4545 1H NMR (300 MHz, CDCl3) δ 7.97 (d, J = 8.1 Hz, 1H), 7.59-7.66 (m, 2H), 7.13 (d, J = 8.1 Hz, 1H), 6.14-6.25 (m, 1H), 6.00-6.11 (m, 1H), 5.29 (d, J = 6.7 Hz, 2H), 4.96 (d, J = 6.7 Hz, 2H), 3.30 (s, 3H), 2.84 (t, J = 6.2 Hz, 2H), 2.47 (t, J = 6.2 Hz, 2H), 2.04-2.15 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.97 (d, J = 8.1 Hz, 1H), 7.59-7.66 (m, 2H), 7.13 (d, J = 8.1 Hz, 1H), 6.14-6.25 (m, 1H), 6.00-6.11 (m, 1H ), 5.29 (d, J = 6.7 Hz, 2H), 4.96 (d, J = 6.7 Hz, 2H), 3.30 (s, 3H), 2.84 (t, J = 6.2 2H), 2.47 (t, J = 6.2 Hz, 2H), 2.04-2.15 (m, 2H) 4646 1H NMR (500 MHz, CDCl3) δ 7.73 (d, 1H, J = 8.4 Hz), 7.67 (s, 2H), 6.95 (d, 1H, J = 8.4 Hz), 4.90 (t, 2H), 4.56 (t, 2H), 3.17 (t, 1H), 2.91 (t, 1H), 2.14-2.28 (m, 3H), 2.03 (m, 1H), 1.91 (s, 3H), 1.76 (m, 2H) ; Mass : 412 1 H NMR (500 MHz, CDCl 3) δ 7.73 (d, 1H, J = 8.4 Hz), 7.67 (s, 2H), 6.95 (d, 1H, J = 8.4 Hz), 4.90 (t, 2H), 4.56 (t, 2H), 3.17 (t, IH), 2.91 (t, IH), 2.14-2.28 (m, 3H), 2.03 (m, IH), 1.91 (s, 3H), 1.76 (m, 2H); Mass: 412 4747 1H NMR (500 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.3 Hz), 7.66 (s, 2H), 6.99 (d, 1H, J = 8.3 Hz), 6.21 (m, 1H), 6.04 (m, 1H), 5.16 (d, 2H), 4.64 (d, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.19 (s, 3H), 2.09 (m, 2H) ; Mass : 445 1 H NMR (500 MHz, CDCl 3) δ 7.86 (d, 1H, J = 8.3 Hz), 7.66 (s, 2H), 6.99 (d, 1H, J = 8.3 Hz), 6.21 (m, 1H), 6.04 2H), 2.19 (s, 3H), 2.09 (m, 2H), 5.16 (d, 2H), 4.64 (d, 2H), 3.26 (s, m, 2H); Mass: 445 4848 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.63-7.70 (m, 2H), 7.12 (d, J = 8.0 Hz, 1H), 5.35 (s, 2H), 4.94 (s, 2H), 3.29 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.45 (t, J = 6.3 Hz, 2H), 2.08 (q, J = 6.1 Hz, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.63-7.70 (m, 2H), 7.12 (d, J = 8.0 Hz, 1H), 5.35 (s, 2H) J = 6.3 Hz, 2 H), 2.45 (t, J = 6.3 Hz, 2H), 2.08 (q, J = 6.1 Hz, 4949 1H NMR (300 MHz, CDCl3) δ 7.88 (d, 1H, J = 8.3 Hz), 7.73 (s, 2H), 7.02 (d, 1H, J = 8.3 Hz), 6.04 (s, 2H), 5.38 (s, 2H), 3.28 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.25 (s, 3H), 2.09 (m, 2H) ; Mass : 434 1 H NMR (300 MHz, CDCl 3) δ 7.88 (d, 1H, J = 8.3 Hz), 7.73 (s, 2H), 7.02 (d, 1H, J = 8.3 Hz), 6.04 (s, 2H), 5.38 (s, 2H), 3.28 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.25 (s, 3H), 2.09 (m, 2H); Mass: 434 5151 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.80 (s, 2H), 7.15 (d, J = 8.3 Hz, 1H), 7.01 (dt, J = 50.6, 6.0 Hz, 1H), 5.09-4.92 (m, 2H), 3.19 (s, 3H), 3.04-3.03 (m, 1H), 2.91-2.89 (m, 1H), 1.99-1.91 (m, 4H), 1.79-1.66 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.80 (s, 2H), 7.15 (d, J = 8.3 Hz, 1H), 7.01 (dt, J = 50.6, 2H), 3.19 (s, 3H), 3.04-3.03 (m, 1H), 2.91-2.89 -1.66 (m, 2H) 5252 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.68 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.2 Hz, 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.21 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.62 (t, J = 6.9 Hz, 1H), 2.52 (t, J = 7.0 Hz, 2H), 2.14 (quin, J = 6.5 Hz, 2H), 1.19 (d, J = 7.0 Hz, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.68 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.2 Hz , 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.21 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.62 (t, J = 6.9 Hz, 1H), 2.52 (t , J = 7.0 Hz, 2H) , 2.14 (quin, J = 6.5 Hz, 2H), 1.19 (d, J = 7.0 Hz, 6H) 5353 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.5 Hz, 1H), 7.68 (s, 2H), 7.45 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz, 2H), 4.70 (t, J = 5.0 Hz, 2H), 3.21 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.15 (s, 3H), 2.14-2.12 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.91 (d, J = 8.5 Hz, 1H), 7.68 (s, 2H), 7.45 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz , 2H), 4.70 (t, J = 5.0 Hz, 2H), 3.21 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.15 (s , ≪ / RTI > 3H), 2.14-2.12 (m, 2H) 5454 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.67 (s, 2H), 7.46 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.1 Hz, 2H), 4.70 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.14 (quin, J = 6.3 Hz, 2H), 1.58-1.57 (m, 1H), 0.99 (s, 4H) 1 H NMR (500 MHz, CDCl 3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.67 (s, 2H), 7.46 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.1 Hz , 2H), 4.70 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.14 (quin , J = 6.3Hz, 2H), 1.58-1.57 (m, IH), 0.99 (s, 4H) 5555 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.95 (t, J = 5.0 Hz, 2H), 4.70 (t, J = 4.8 Hz, 2H), 3.19 (s, 3H), 2.73 (t, J = 6.1 Hz, 2H), 2.50 (t, J = 6.4 Hz, 2H), 2.13 (quin, J = 6.7 Hz, 2H), 1.20 (s, 9H) 1 H NMR (500 MHz, CDCl 3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.95 (t, J = 5.0 Hz , 2H), 4.70 (t, J = 4.8 Hz, 2H), 3.19 (s, 3H), 2.73 (t, J = 6.1 Hz, 2H), 2.50 (t, J = 6.4 Hz, 2H), 2.13 (quin , J = 6.7 Hz, 2H), 1.20 (s, 9H) 5656 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 15.8 Hz, 2H), 7.50 (d, J = 8.2 Hz, 1H), 4.91 (t, J = 5.0 Hz, 2H), 4.65 (t, J = 5.0 Hz, 2H), 3.08 (s, 3H), 2.75 (t, J = 5.2 Hz, 2H), 2.63 (sep, J = 6.9 Hz, 1H), 2.52 (t, J = 4.6 Hz, 2H), 2.14 (quin, J = 6.7 Hz, 2H), 1.19 (d, J = 7.1 Hz, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 15.8 Hz, 2H), 7.50 (d, J = 8.2 Hz, 1H), 4.91 (t , J = 5.0 Hz, 2H) , 4.65 (t, J = 5.0 Hz, 2H), 3.08 (s, 3H), 2.75 (t, J = 5.2 Hz, 2H), 2.63 (sep, J = 6.9 Hz, 1H ), 2.52 (t, J = 4.6 Hz, 2H), 2.14 (quin, J = 6.7 Hz, 2H), 1.19 (d, J = 7.1 Hz, 6H) 5757 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.69 (s, 2H), 7.38 (d, J = 8.2 Hz, 1H), 4.97 (t, J = 5.1 Hz, 2H), 4.70 (t, J = 5.2 Hz, 2H), 3.21 (s, 3H), 3.07-3.05 (m, 2H), 2.32-2.17 (m, 4H), 1.76-1.75 (m, 3H), 1.08-1.04 (m, 4H) 1 H NMR (500 MHz, CDCl 3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.69 (s, 2H), 7.38 (d, J = 8.2 Hz, 1H), 4.97 (t, J = 5.1 Hz 2H), 4.70 (t, J = 5.2 Hz, 2H), 3.21 (s, 3H), 3.07-3.05 (m, 2H), 2.32-2.17 (m, 4H), 1.76-1.75 1.08-1.04 (m, 4H) 5858 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.68 (s, 2H), 7.37 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz, 2H), 4.69 (t, J = 5.3 Hz, 2H), 3.20 (s, 3H), 3.04-3.03 (m, 2H), 2.66 (quin, J = 6.9 Hz, 1H), 2.21-2.20 (m, 4H), 1.76-1.73 (m, 2H), 1.27-1.22 (m, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.68 (s, 2H), 7.37 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz 2H), 4.69 (t, J = 5.3 Hz, 2H), 3.20 (s, 3H), 3.04-3.03 (m, 2H), 2.66 (quin, J = 6.9 Hz, 1H) 4H), 1.76-1.73 (m, 2H), 1.27-1.22 (m, 6H) 5959 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.34 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.69 (t, J = 5.2 Hz, 2H), 3.20 (s, 3H), 3.06-3.00 (m, 2H), 2.19 (s, 3H), 2.15-1.73 (m, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.34 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.69 (t, J = 5.2 Hz, 2H), 3.20 (s, 3H), 3.06-3.00 (m, 2H), 2.19 (s, 3H), 2.15-1.73 (m, 6H) 6060 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.39 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.70 (t, J = 5.1 Hz, 2H), 3.23 (s, 3H), 3.01 (q, J = 6.6 Hz, 2H), 2.33-2.19 (m, 4H), 1.76-1.73 (m, 2H), 1.24 (s, 9H). 1 H NMR (500 MHz, CDCl 3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.39 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz 2H), 4.70 (t, J = 5.1 Hz, 2H), 3.23 (s, 3H), 3.01 (q, J = 6.6 Hz, 2H), 2.33-2.19 (m, 4H), 1.76-1.73 2H), 1.24 (s, 9H). 6161 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.11 (d, J = 8.0 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.37 (t, J = 4.4 Hz, 2H), 4.14-1.12 (m, 2H), 3.89 (t, J = 4.5 Hz, 2H), 3.28 (s, 3H), 3.19 (t, J = 5.4 Hz, 1H), 2.92 (t, J = 6.4 Hz, 1H), 2.26-1.76 (m, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.95 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.11 (d, J = 8.0 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.37 (t, J = 4.4 Hz, 2H), 4.14-1.12 (m, 2H), 3.89 (t, J = 4.5 Hz, 2H), 3.28 (s, 3H), 3.19 (t, J = 5.4 Hz, 1H), 2.92 (t, J = 6.4 Hz, 1H), 2.26-1.76 (m, 6H) 6262 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.33 (d, J = 8.1 Hz, 1H), 4.68 (t, J = 5.7 Hz, 2H), 4.34 (t, J = 4.5 Hz, 2H), 4.13-4.11 (m, 2H), 3.88-3.87 (t, J = 4.4 Hz, 2H), 3.25 (s, 3H), 3.07-3.01 (m, 2H), 2.18 (s, 3H), 2.15-1.73 (m, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.33 (d, J = 8.1 Hz, 1H), 4.68 (t, J = 5.7 Hz 2H), 4.34 (t, J = 4.5 Hz, 2H), 4.13-4. 11 (m, 2H), 3.88-3.87 (t, J = 4.4 Hz, 2H) m, 2H), 2.18 (s, 3H), 2.15 - 1.73 (m, 6H) 6363 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.61 (s, 2H), 7.30 (d, J = 8.2 Hz, 1H), 4.67 (t, J = 5.6 Hz, 2H), 4.33 (t, J = 4.1 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 3.86 (t, J = 4.3 Hz, 2H), 3.24 (s, 3H), 3.05-3.04 (m, 2H), 2.16- 2.07 (m, 4H), 1.75-1.59 (m, 3H), 1.04-1.01 (m, 4H) 1 H NMR (300 MHz, CDCl 3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.61 (s, 2H), 7.30 (d, J = 8.2 Hz, 1H), 4.67 (t, J = 5.6 Hz , 2H), 4.33 (t, J = 4.1 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 3.86 (t, J = 4.3 Hz, 2H), 3.24 (s, 3H), 3.05-3.04 (m, 2H), 2.16-2.07 (m, 4H), 1.75-1.59 (m, 3H), 1.04-1.01 6464 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.37 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.35 (t, J = 4.2 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.5 Hz, 2H), 3.26 (s, 3H), 3.05-3.04 (m, 2H), 2.34-2.32 (m, 1H), 2.16-2.13 (m, 4H), 1.77-1.75 (m, 2H), 1.27-1.21 (m, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.37 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.35 (t, J = 4.2 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.5 Hz, 2H), 3.26 (s, 3H), 3.05-3.04 (m, 2H), 2.34-2.32 (m, 1H), 2.16-2.13 (m, 4H), 1.77-1.75 6565 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.38 (d, J = 8.1 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.35 (t, J = 4.1 Hz, 2H), 4.13 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 2.7 Hz, 2H), 3.25 (s, 3H), 3.01-3.00 (m, 2H), 2.33-2.13 (m, 4H), 1.80-1.74 (m, 2H), 1.24 (s, 9H). 1 H NMR (500 MHz, CDCl 3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.38 (d, J = 8.1 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.35 (t, J = 4.1 Hz, 2H), 4.13 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 2.7 Hz, 2H), 3.25 (s, 3H), 3.01-3.00 (m, 2H), 2.33-2.13 (m, 4H), 1.80-1.74 (m, 2H), 1.24 (s, 9H). 6666 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.67 (s, 2H), 7.35 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.69-4.67 (m, 2H), 3.20 (s, 3H), 3.05 (t, J = 5.0 Hz, 1H), 3.01 (t, J = 4.8 Hz, 1H), 2.44-2.43 (m, 2H), 2.29-2.05 (m, 4H), 1.76-1.72 (m, 2H), 1.15 (t, J = 4.2 Hz, 3H). 1 H NMR (500 MHz, CDCl 3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.67 (s, 2H), 7.35 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz (M, 2H), 4.69-4.67 (m, 2H), 3.20 (s, 3H), 3.05 (t, J = 5.0 Hz, 1H), 3.01 (t, J = 4.8 Hz, 1H) 2H), 2.29-2.05 (m, 4H), 1.76-1.72 (m, 2H), 1.15 (t, J = 4.2 Hz, 3H). 6767 1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.6 Hz, 2H), 3.26 (s, 3H), 2.77 (t, J = 6.2 Hz, 2H), 2.54 (t, J = 6.5 Hz, 2H), 2.17 (s, 3H), 2.15-2.14 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.6 Hz, 2H), 3.26 (s, 3H), 2.77 (t , J = 6.2 Hz, 2H) , 2.54 (t, J = 6.5 Hz, 2H), 2.17 (s, 3H), 2.15-2.14 (m, 2H) 6868 1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.1 Hz, 1H), 4.70 (t, J = 5.6 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.13 (t, J = 5.7 Hz, 2H), 3.89 (t, J = 4.6 Hz, 2H), 3.27 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.53 (t, J = 6.5 Hz, 2H), 2.14-2.13 (m, 2H) 1.27-1.26 (m, 1H), 0.99-0.97 (m, 4H) 1 H NMR (500 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.1 Hz, 1H), 4.70 (t, J = 5.6 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.13 (t, J = 5.7 Hz, 2H), 3.89 (t, J = 4.6 Hz, 2H), 3.27 (s, 3H), 2.75 (t , J = 6.2 Hz, 2H) , 2.53 (t, J = 6.5 Hz, 2H), 2.14-2.13 (m, 2H) 1.27-1.26 (m, 1H), 0.99-0.97 (m, 4H) 6969 1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.1 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.89 (t, J = 4.4 Hz, 2H), 3.26 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.61 (t, J = 6.9 Hz, 1H), 2.53 (t, J = 7.0 Hz, 2H), 2.15 (quin, J = 6.4 Hz, 2H), 1.18 (d, J = 7.1 Hz, 6H). 1 H NMR (500 MHz, CDCl 3) δ 7.93 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.1 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.89 (t, J = 4.4 Hz, 2H), 3.26 (s, 3H), 2.76 (t , J = 6.2 Hz, 2H) , 2.61 (t, J = 6.9 Hz, 1H), 2.53 (t, J = 7.0 Hz, 2H), 2.15 (quin, J = 6.4 Hz, 2H), 1.18 (d, J = 7.1 Hz, 6H). 7070 1H NMR (500 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.48 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.26 (s, 3H), 2.75 (t, J = 6.1 Hz, 2H), 2.53 (t, J = 6.1 Hz, 2H), 2.15 (quin, J = 6.5 Hz, 2H), 1.20-2.06 (m, 9H). 1 H NMR (500 MHz, CDCl 3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.48 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.26 (s, 3H), 2.75 (t J = 6.1 Hz, 2H), 2.53 (t, J = 6.1 Hz, 2H), 2.15 (quin, J = 6.5 Hz, 2H), 1.20-2.06 (m, 9H). 7171 1H NMR (300 MHz, CDCl3) δ 7.82 (d, 1H, J = 8.3 Hz), 7.68 (s, 2H), 7.36 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.53 (t, 2H), 3.23 (s, 3H), 2.75 (t, 2H), 2.50 (t, 2H), 2.18 (s, 3H), 2.14 (m, 2H), 2.08 (s, 3H) ; Mass : 461 1 H NMR (300 MHz, CDCl 3) δ 7.82 (d, 1H, J = 8.3 Hz), 7.68 (s, 2H), 7.36 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.53 (t, 2H), 3.23 (s, 3H), 2.75 (t, 2H), 2.50 (t, 2H), 2.18 (s, 3H), 2.14 (m, 2H), 2.08 Mass: 461 7272 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.44 (d, J = 8.1 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.4 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.76 (t, J = 5.8 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 3H), 2.14 (s, 3H) 1 H NMR (300 MHz, CDCl 3) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.44 (d, J = 8.1 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.12 (m, 1H ), 5.14 (d, J = 5.4 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.76 (t, J = 5.8 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 3H), 2.14 (s, 7373 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.3 Hz, 1H), 7.61-7.67 (m, 2H), 7.46 (d, J = 8.2 Hz, 1H), 6.15-6.25 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.3 Hz, 2H), 4.74 (d, J = 5.3 Hz, 2H), 3.24 (s, 3H), 2.75 (t, J = 6.0 Hz, 2H), 2.52 (t, J = 6.5 Hz, 2H), 2.07-2.18 (m, 2H), 1.53-1.60 (m, 1H), 0.94-1.03 (m, 4H) 1 H NMR (300 MHz, CDCl 3) δ 7.92 (d, J = 8.3 Hz, 1H), 7.61-7.67 (m, 2H), 7.46 (d, J = 8.2 Hz, 1H), 6.15-6.25 (m, 1H), 5.99-6.12 (m, 1H ), 5.14 (d, J = 5.3 Hz, 2H), 4.74 (d, J = 5.3 Hz, 2H), 3.24 (s, 3H), 2.75 (t, J = 6.0 Hz, 2H), 2.52 (t , J = 6.5 Hz, 2H), 2.07-2.18 (m, 2H), 1.53-1.60 (m, 1H), 0.94-1.03 (m, 4H) 7474 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.60-7.65 (m, 2H), 7.47 (d, J = 8.3 Hz, 1H), 6.15-6.26 (m, 1H), 5.99-6.10 (m, 1H), 5.14 (d, J = 6.0 Hz, 2H), 4.75 (d, J = 6.0 Hz, 2H), 3.23 (s, 3H), 2.73 (t, J = 6.0 Hz, 2H), 2.51 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 2H), 1.19 (s, 9H) 1 H NMR (300 MHz, CDCl 3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.60-7.65 (m, 2H), 7.47 (d, J = 8.3 Hz, 1H), 6.15-6.26 (m, 1H), 5.99-6.10 (m, 1H ), 5.14 (d, J = 6.0 Hz, 2H), 4.75 (d, J = 6.0 Hz, 2H), 3.23 (s, 3H), 2.73 (t, J = 6.0 2H, J = 6.4 Hz, 2H), 2.08-2.20 (m, 2H), 1.19 (s, 9H) 7575 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.62-7.66 (m, 2H), 7.46 (d, J = 8.2 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.74 (t, J = 6.1 Hz, 2H), 2.55-2.65 (m, 1H), 2.52 (t, J = 6.3 Hz, 2H), 2.08-2.19 (m, 2H), 1.16 (d, J = 7.0 Hz, 6H) 1 H NMR (300 MHz, CDCl 3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.62-7.66 (m, 2H), 7.46 (d, J = 8.2 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.11 (m, 1H ), 5.14 (d, J = 5.6 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.74 (t, J = 6.1 2H), 1.16 (d, J = 7.0 Hz, 6H), 2.52 (t, J = 6.3 Hz, 2H), 2.55-2.65 7676 1H NMR (300 MHz, CDCl3) δ 7.80 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 7.26 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.52 (t, 2H), 3.21 (s, 3H), 3.03 (t, 1H), 2.99 (t, 1H), 2.30 (m, 1H), 2.19 (m, 2H), 2.13 (s, 3H), 2.11 (s, 3H), 2.10 (m, 1H), 1.74 (m, 2H) ; Mass : 487 1 H NMR (300 MHz, CDCl 3) δ 7.80 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 7.26 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.52 (m, 2H), 2.13 (s, 3H), 2.11 (m, 2H), 3.21 (s, s, 3H), 2.10 (m, IH), 1.74 (m, 2H); Mass: 487 7777 1H NMR (300 MHz, CDCl3) δ 7.69 (s, 2H), 7.62 (d, 1H, J = 8.5 Hz), 7.31 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.53 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.17 (s, 3H), 2.15 (m, 2H), 2.08 (s, 3H) ; Mass : 428 1 H NMR (300 MHz, CDCl 3) δ 7.69 (s, 2H), 7.62 (d, 1H, J = 8.5 Hz), 7.31 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.53 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.17 (s, 3H), 2.15 (m, 2H), 2.08 (s, 3H); Mass: 428 7878 1H NMR (300 MHz, CDCl3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.13-6.25 (m, 1H), 6.01-6.13 (m, 1H), 5.30 (d, J = 6.2 Hz, 2H), 4.95 (d, J = 6.7 Hz, 2H), 3.29 (s, 3H), 2.79 (t, J = 6.0 Hz, 2H), 2.55 (t, J = 6.2 Hz, 2H), 2.09-2.23 (m, 5H) 1 H NMR (300 MHz, CDCl 3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.13-6.25 (m, 1H), 6.01-6.13 (m, 1H ), 5.30 (d, J = 6.2 Hz, 2H), 4.95 (d, J = 6.7 Hz, 2H), 3.29 (s, 3H), 2.79 (t, J = 6.0 Hz, 2H), 2.55 (t, J = 6.2 Hz, 2H), 2.09-2.23 (m, 5H) 7979 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.12-6.23 (m, 1H), 6.00-6.11 (m, 1H), 5.28 (d, J = 6.7 Hz, 2H), 4.93 (d, J = 6.9 Hz, 2H), 3.27 (s, 3H), 2.76 (t, J = 6.0 Hz, 2H), 2.56-2.67 (m, 1H), 2.53 (t, J = 6.2 Hz, 2H), 2.09-2.20 (m, 2H), 1.18 (d, J = 6.9 Hz, 6H) 1 H NMR (300 MHz, CDCl 3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.12-6.23 (m, 1H), 6.00-6.11 (m, 1H ), 5.28 (d, J = 6.7 Hz, 2H), 4.93 (d, J = 6.9 Hz, 2H), 3.27 (s, 3H), 2.76 (t, J = 6.0 Hz, 2H), 2.56-2.67 (m , 1H), 2.53 (t, J = 6.2 Hz, 2H), 2.09-2.20 (m, 2H), 1.18 (d, J = 6.9 Hz, 6H) 8080 1H NMR (300 MHz, CDCl3) δ 7.83 (d, 1H, J = 8.2 Hz), 7.64 (s, 2H), 7.35 (d, 1H, J = 8.2 Hz), 6.19 (m, 1H), 6.03 (m, 1H), 5.14 (d, 2H), 4.58 (d, 2H), 3.22 (s, 3H), 2.75 (t, 2H), 2.50 (t, 2H), 2.41 (s, 3H), 2.15 (m, 2H), 2.07 (s, 3H) ; Mass : 487 1 H NMR (300 MHz, CDCl 3) δ 7.83 (d, 1H, J = 8.2 Hz), 7.64 (s, 2H), 7.35 (d, 1H, J = 8.2 Hz), 6.19 (m, 1H), 6.03 2H), 2.41 (s, 3H), 2.15 (m, 2H), 5.14 (d, 2H), 4.58 (d, 2H), 3.22 (s, m, 2 H), 2.07 (s, 3 H); Mass: 487 8181 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.0 Hz, 1H), 7.65-7.70 (m, 2H), 7.49 (d, J = 8.0 Hz, 1H), 5.36 (s, 2H), 4.95 (s, 2H), 3.29 (s, 3H), 2.78 (t, J = 6.3 Hz, 1H), 2.54 (d, J = 6.7 Hz, 1H), 2.17 (s, 3H), 2.13-2.18 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.94 (d, J = 8.0 Hz, 1H), 7.65-7.70 (m, 2H), 7.49 (d, J = 8.0 Hz, 1H), 5.36 (s, 2H) , 4.95 (s, 2H), 3.29 (s, 3H), 2.78 (t, J = 6.3 Hz, 1H), 2.54 (d, J = 6.7 Hz, 1H), 2.17 (s, 3H), 2.13-2.18 ( m, 2H) 8282 1H NMR (500 MHz, CDCl3) δ 7.66 (s, 2H), 7.60 (d, 1H, J = 8.4 Hz), 7.20 (d, 1H, J = 8.4 Hz), 4.87 (t, 2H), 4.50 (t, 2H), 3.03 (t, 1H), 3.01 (t, 1H), 2.10-2.31 (m, 4H), 2.11 (s, 3H), 2.10 (s, 3H), 1.75 (m, 2H) ; Mass : 454 1 H NMR (500 MHz, CDCl 3) δ 7.66 (s, 2H), 7.60 (d, 1H, J = 8.4 Hz), 7.20 (d, 1H, J = 8.4 Hz), 4.87 (t, 2H), 4.50 (t, 2H), 3.03 (t, IH), 3.01 (t, IH), 2.10-2.31 (m, 4H), 2.11 (s, 3H), 2.10 (s, 3H), 1.75 (m, 2H); Mass: 454 8383 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.40 (d, J = 8.2 Hz, 1H), 7.01 (dt, J = 50.9, 5.8 Hz, 1H), 5.07-4.95 (m, 2H), 3.20 (s, 3H), 3.10-3.01 (m, 2H), 2.23 (s, 3H), 2.21-2.13 (m, 4H), 1.84-1.72 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.40 (d, J = 8.2 Hz, 1H), 7.01 (dt, J = 50.9, 3H), 2.23 (s, 3H), 2.21-2.13 (m, 4H), 1.84-1.72 (m, 2H) (m, 2H) 8484 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 7.02 (dt, J = 50.8, 5.9 Hz, 1H), 5.07-4.98 (m, 2H), 3.06-3.00 (m, 2H), 2.21-2.16 (m, 4H), 1.80-1.74 (m, 2H), 1.27 (s, 9H) 1 H NMR (300 MHz, CDCl 3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 7.02 (dt, J = 50.8, 2H), 1.27 (s, 9H), 2.9-2. 16 (m, 2H) 8585 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.86 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.3 Hz, 2H), 2.15 (quin, J = 6.8 Hz, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.86 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.3 Hz, 2H), 2.15 (quin , ≪ / RTI > J = 6.8 Hz, 2H) 8686 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.3 Hz, 1H), 7.61 (s, 2H), 7.56 (d, J = 8.3 Hz, 1H), 4.58 (t, J = 7.0 Hz, 2H), 4.26 (t, J = 6.2 Hz, 2H), 3.24 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.26-2.16 (m, 4H), 1.93-1.88 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.3 Hz, 1H), 7.61 (s, 2H), 7.56 (d, J = 8.3 Hz, 1H), 4.58 (t, J = 7.0 Hz , 2H), 4.26 (t, J = 6.2 Hz, 2H), 3.24 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.26-2.16 (m, 4 H), 1.93 - 1.88 (m, 2 H) 8787 1H NMR (300 MHz, CDCl3) δ 8.20 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 4.60-4.66 (m, 4H), 3.16 (s, 3H), 2.92 (t, J = 6.1 Hz, 2H), 2.56 (t, J = 6.1 Hz, 2H), 2.16-2.33 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.20 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 4.60-4.66 (m, 4H) , 3.16 (s, 3H), 2.92 (t, J = 6.1 Hz, 2H), 2.56 (t, J = 6.1 Hz, 2H), 2.16-2.33 (m, 2H) 8888 1H NMR (500 MHz, CDCl3) δ 8.19 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.61 (d, J = 8.2 Hz, 1H), 4.66 (t, J = 4.8 Hz, 2H), 4.62 (t, J = 4.5 Hz, 2H), 3.15 (s, 3H), 2.91 (t, J = 6.1 Hz, 2H), 2.56 (t, J = 7.0 Hz, 2H), 2.19 (quin, J = 6.4 Hz, 2H) 1 H NMR (500 MHz, CDCl 3) δ 8.19 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.61 (d, J = 8.2 Hz, 1H), 4.66 (t, J = 4.8 Hz , 2H), 4.62 (t, J = 4.5 Hz, 2H), 3.15 (s, 3H), 2.91 (t, J = 6.1 Hz, 2H), 2.56 (t, J = 7.0 Hz, 2H), 2.19 (quin , J = 6.4 Hz, 2H) 8989 1H NMR (500 MHz, CDCl3) δ 8.39 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.62 (d, J = 8.2 Hz, 1H), 4.75 (t, J = 4.8 Hz, 2H), 4.65 (t, J = 4.6 Hz, 2H), 3.12 (s, 3H), 2.90 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.18 (quin, J = 6.7 Hz, 2H) 1 H NMR (500 MHz, CDCl 3) δ 8.39 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.62 (d, J = 8.2 Hz, 1H), 4.75 (t, J = 4.8 Hz , 2H), 4.65 (t, J = 4.6 Hz, 2H), 3.12 (s, 3H), 2.90 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.18 (quin , ≪ / RTI > J = 6.7 Hz, 2H) 9090 1H NMR (300 MHz, CDCl3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 3.6 Hz, 2H), 7.60 (d, J = 8.2 Hz, 1H), 4.92 (t, J = 4.9 Hz, 2H), 4.66 (t, J = 4.9 Hz, 2H)), 3.10 (s, 3H), 2.89 (t, J = 6.0 Hz, 2H), 2.54 (t, J = 6.4 Hz, 2H), 2.18 (quin, J = 6.4 Hz, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 3.6 Hz, 2H), 7.60 (d, J = 8.2 Hz, 1H), 4.92 (t , J = 4.9 Hz, 2H) , 4.66 (t, J = 4.9 Hz, 2H)), 3.10 (s, 3H), 2.89 (t, J = 6.0 Hz, 2H), 2.54 (t, J = 6.4 Hz, 2H), 2.18 (quin, J = 6.4 Hz, 2H) 9191 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.62 (s, 2H), 7.57 (d, J = 8.3 Hz, 1H), 4.69 (t, J = 5.7 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.26 (S, 3H), 2.89 (t, J = 6.2 Hz, 2H), 2.55 (t, J = 6.5 Hz, 2H), 2.20-2.17 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.62 (s, 2H), 7.57 (d, J = 8.3 Hz, 1H), 4.69 (t, J = 5.7 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.26 (S, 3H), 2.89 (t 2H, J = 6.2 Hz, 2H), 2.55 (t, J = 9292 1H NMR (500 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz, 2H), 4.70 (t, J = 4.9 Hz, 2H), 3.23-3.22 (m, 1H), 3.21 (s, 3H), 3.06-3.05 (m, 1H), 2.31-2.23 (m, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz 2H), 4.70 (t, J = 4.9 Hz, 2H), 3.23-3.22 (m, 1H), 3.21 (s, 3H), 3.06-3.05 9393 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.57 (d, J = 8.2 Hz, 1H), 4.75 (t, J = 7.1 Hz, 2H), 4.31 (t, J = 5.9 Hz, 2H), 3.27 (s, 3H), 2.89 (t, J = 6.0 Hz, 2H), 2.52 (m, 4H), 2.18 (quin, J = 6.4 Hz, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.57 (d, J = 8.2 Hz, 1H), 4.75 (t, J = 7.1 Hz , 2H), 4.31 (t, J = 5.9 Hz, 2H), 3.27 (s, 3H), 2.89 (t, J = 6.0 Hz, 2H), 2.52 (m, 4H), 2.18 (quin, J = 6.4 Hz , 2H) 9494 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.35 (t, J = 4.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.27 (S, 3H), 3.24 (t, J = 4.8 Hz, 1H), 3.07 (t, J = 6.5 Hz, 1H), 2.34-1.95 (m, 6H) 1 H NMR (500 MHz, CDCl 3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.35 (t, J = 4.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.27 (S, 3H), 3.24 (t J = 4.8 Hz, 1H), 3.07 (t, J = 6.5 Hz, 1H), 2.34-1.95 (m, 6H) 9595 1H NMR (300 MHz, CDCl3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.71 (s, 2H), 7.39 (d, 1H, J = 8.3 Hz), 4.95 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.90 (t, 2H), 2.54 (t, 2H), 2.30 (s, 3H), 2.22 (m, 2H) ; Mass : 437.5 1 H NMR (300 MHz, CDCl 3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.71 (s, 2H), 7.39 (d, 1H, J = 8.3 Hz), 4.95 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.90 (t, 2H), 2.54 (t, 2H), 2.30 (s, 3H), 2.22 (m, 2H); Mass: 437.5 9696 1H NMR (300 MHz, CDCl3) δ 7.84 (d, 1H, J = 8.3 Hz), 7.69 (s, 2H), 7.26 (d, 1H, J = 8.3 Hz), 4.93 (t, 2H), 4.54 (t, 2H), 3.24 (s, 3H), 3.21 (t, 1H), 3.06 (t, 1H), 2.32 (m, 1H), 2.25 (s, 3H), 2.23 (m, 1H), 2.06-2.17 (m, 2H), 1.77 (m, 2H) ; Mass : 463.5 1 H NMR (300 MHz, CDCl 3) δ 7.84 (d, 1H, J = 8.3 Hz), 7.69 (s, 2H), 7.26 (d, 1H, J = 8.3 Hz), 4.93 (t, 2H), 4.54 (s, 3H), 2.23 (m, 1H), 2.06 (t, 2H), 3.24 2.17 (m, 2 H), 1.77 (m, 2 H); Mass: 463.5 9797 1H NMR (300 MHz, CDCl3) δ 7.69 (s, 2H), 7.63 (d, 1H, J = 8.5 Hz), 7.32 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.54 (t, 2H), 2.88 (t, 2H), 2.55 (t, 2H), 2.25 (s, 3H), 2.20 (m, 2H) ; Mass : 404.5 1 H NMR (300 MHz, CDCl 3) δ 7.69 (s, 2H), 7.63 (d, 1H, J = 8.5 Hz), 7.32 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.54 (t, 2H), 2.88 (t, 2H), 2.55 (t, 2H), 2.25 (s, 3H), 2.20 (m, 2H); Mass: 404.5 9898 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.2 Hz), 7.64 (s, 2H), 7.37 (d, 1H, J = 8.2 Hz), 6.21 (m, 1H), 6.03 (m, 1H), 5.15 (d, 2H), 4.59 (d, 2H), 3.23 (s, 3H), 2.88 (t, 2H), 2.54 (t, 2H), 2.52 (s, 3H), 2.19 (m, 2H) ; Mass : 463.5 1 H NMR (300 MHz, CDCl 3) δ 7.86 (d, 1H, J = 8.2 Hz), 7.64 (s, 2H), 7.37 (d, 1H, J = 8.2 Hz), 6.21 (m, 1H), 6.03 2H), 2.52 (s, 3H), 2.19 (d, 2H), 5.19 (d, m, 2H); Mass: 463.5 9999 1H NMR (300 MHz, CDCl3) δ 7.99 (d, J = 8.3 Hz, 1H), 7.82 (s, 2H), 7.53 (d, J = 8.3 Hz, 1H), 7.11 (dt, J = 50.9, 5.9 Hz, 1H), 5.07-4.96 (m, 2H), 3.28-3.24 (m, 1H), 3.21 (s, 3H), 3.09-3.05 (m, 1H), 2.29-2.09 (m, 4H), 1.86-1.75 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.99 (d, J = 8.3 Hz, 1H), 7.82 (s, 2H), 7.53 (d, J = 8.3 Hz, 1H), 7.11 (dt, J = 50.9, 3H), 3.09-3.05 (m, 1H), 2.29-2.09 (m, 4H), 1.86 (m, 2H) -1.75 (m, 2 H) 100100 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 7.9 Hz, 1H), 7.81 (d, J = 11.8 Hz, 2H), 7.52 (d, J = 7.9 Hz, 1H), 4.93 (d, J = 4.8 Hz, 2H), 4.67 (t, J = 4.8 Hz, 2H), 3.09 (s, 3H), 2.75 (t, J = 6.1 Hz, 2H), 2.53 (t, J = 6.6 Hz, 2H), 2.12-2.19 (m, 2H), 1.23 (s, 9H) 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 7.9 Hz, 1H), 7.81 (d, J = 11.8 Hz, 2H), 7.52 (d, J = 7.9 Hz, 1H), 4.93 (d , J = 4.8 Hz, 2H) , 4.67 (t, J = 4.8 Hz, 2H), 3.09 (s, 3H), 2.75 (t, J = 6.1 Hz, 2H), 2.53 (t, J = 6.6 Hz, 2H ), 2.12-2.19 (m, 2H), 1.23 (s, 9H) 101101 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 7.8 Hz, 1H), 7.79-7.87 (m, 1H), 7.67-7.76 (m, 1H), 7.47 (d, J = 7.8 Hz, 1H), 4.65 (t, J = 4.6 Hz, 2H), 4.39 (t, J = 3.7 Hz, 2H), 3.98 (t, J = 4.6 Hz, 2H), 3.90 (t, J = 3.7 Hz, 2H), 3.23 (s, 3H), 2.79 (t, J = 5.9 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.12-2.22 (m, 5H) 1 H NMR (300 MHz, CDCl 3) δ 7.95 (d, J = 7.8 Hz, 1H), 7.79-7.87 (m, 1H), 7.67-7.76 (m, 1H), 7.47 (d, J = 7.8 Hz, 1H), 4.65 (t, J = 4.6 Hz, 2H), 4.39 (t, J = 3.7 Hz, 2H), 3.98 (t, J = 4.6 Hz, 2H), 3.90 (t, J = 3.7 Hz, 2H) , 3.23 (s, 3H), 2.79 (t, J = 5.9 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.12-2.22 102102 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.80-7.85 (m, 1H), 7.69-7.74 (m, 1H), 7.49 (d, J = 8.2 Hz, 1H), 4.66 (t, J = 4.9 Hz, 2H), 4.39 (t, J = 4.1 Hz, 2H), 3.98 (t, J = 4.9 Hz, 2H), 3.90 (t, J = 4.1 Hz, 2H), 3.23 (s, 3H), 2.78 (t, J = 6.2 Hz, 2H), 2.55 (t, J = 6.6 Hz, 2H), 2.12-2.19 (m, 2h), 1.59-1.67 (m, 1H), 0.98-1.05 (m, 4H) 1 H NMR (300 MHz, CDCl 3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.80-7.85 (m, 1H), 7.69-7.74 (m, 1H), 7.49 (d, J = 8.2 Hz, 1H), 4.66 (t, J = 4.9 Hz, 2H), 4.39 (t, J = 4.1 Hz, 2H), 3.98 (t, J = 4.9 Hz, 2H), 3.90 (t, J = 4.1 Hz, 2H) 1H), 3.23 (s, 3H), 2.78 (t, J = 6.2 Hz, 2H), 2.55 (t, J = 6.6 Hz, 2H), 2.12-2.19 0.98-1.05 (m, 4H) 103103 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.5 Hz, 1H), 7.82-7.85 (m, 1H). 7.71-7.73 (m, 1H), 7.37 (d, J = 8.5 Hz, 1H), 4.65 (t, J = 4.7 Hz, 2H), 4.39 (t, J = 4.7 Hz, 2H), 3.98 (t, J = 4.7 Hz, 2H), 3.90 (t, J = 4.7 Hz, 2H), 3.23 (s, 3H), 3.07-3.11 (m, 1H), 3.02-3.06 (m, 1H), 2.31-2.36 (m, 1H), 2.14-2.26 (m, 6H), 1.74-1.85 (m, 2H) 1 H NMR (300 MHz, CDCl 3 )? 7.94 (d, J = 8.5 Hz, 1 H), 7.82-7.85 (m, 1H). 7.71-7.73 (m, 1H), 7.37 (d, J = 8.5 Hz, 1H), 4.65 (t, J = 4.7 Hz, 2H), 4.39 (t, J = 4.7 Hz, 2H), 3.98 (t, J 2H), 3.90 (t, J = 4.7 Hz, 2H), 3.23 (s, 3H), 3.07-3.11 (m, 1H), 2.14-2.26 (m, 6H), 1.74-1.85 (m, 2H) 104104 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.66-7.70 (m, 2H), 7.51 (d, J = 8.2 Hz, 1H), 5.36 (s, 2H), 4.94 (s, 2H), 2.76 (t, J = 6.1 Hz, 2H), 2.57-2.69 (m, 1H), 2.53 (t, J = 6.4 Hz, 2H), 2.10-2.20 (m, 2H), 1.19 (d, J = 6.9 Hz, 6H) 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.66-7.70 (m, 2H), 7.51 (d, J = 8.2 Hz, 1H), 5.36 (s, 2H) , 4.94 (s, 2H), 2.76 (t, J = 6.1 Hz, 2H), 2.57-2.69 (m, 1H), 2.53 (t, J = 6.4 Hz, 2H), 2.10-2.20 (m, 2H), 1.19 (d, J = 6.9 Hz, 6 H) 105105 1H NMR (300 MHz, CDCl3) δ 7.61 (d, 1H, J = 8.4 Hz), 7.60 (s, 2H), 7.32 (d, 1H, J = 8.4 Hz), 5.97-6.11 (m, 2H), 5.17 (d, 2H), 4.73 (d, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.49 (s, 3H), 2.15 (m, 2H), 2.09 (s, 3H) ; Mass : 454 1 H NMR (300 MHz, CDCl 3) δ 7.61 (d, 1H, J = 8.4 Hz), 7.60 (s, 2H), 7.32 (d, 1H, J = 8.4 Hz), 5.97-6.11 (m, 2H) , 5.17 (d, 2H), 4.73 (d, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.49 (s, 3H), 2.15 (m, 2H), 2.09 Mass: 454 106106 1H NMR (300 MHz, CDCl3) δ 7.68 (s, 2H), 7.62 (d, 1H, J = 8.4 Hz), 7.32 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.54 (d, 2H), 2.77 (t, 2H), 2.53 (t, 2H), 2.45 (s, 3H), 2.14 (m, 2H), 2.09 (s, 3H) ; Mass : 454 1 H NMR (300 MHz, CDCl 3) δ 7.68 (s, 2H), 7.62 (d, 1H, J = 8.4 Hz), 7.32 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 2H), 2.14 (m, 2H), 2.09 (m, 2H), 5.13 (d, 2H) s, 3H); Mass: 454 107107 1H NMR (300 MHz, CDCl3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.41 (d, 1H, J = 8.2 Hz), 6.18 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.79 (d, 2H), 3.28 (s, 3H), 2.79 (t, 2H), 2.54 (t, 2H), 2.48 (s, 3H), 2.18 (m, 2H), 2.11 (s, 3H) ; Mass : 487 1 H NMR (300 MHz, CDCl 3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.41 (d, 1H, J = 8.2 Hz), 6.18 (m, 1H), 6.06 2H), 2.48 (s, 3H), 2.18 (m, 2H), 5.27 (d, 2H) m, 2 H), 2.11 (s, 3 H); Mass: 487 108108 1H NMR (300 MHz, CDCl3) δ 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 6.93 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.56 (d, 2H), 2.83 (t, 2H), 2.46 (t, 2H), 2.20 (s, 3H), 2.08 (m, 2H) ; Mass : 412 1 H NMR (300 MHz, CDCl 3) δ 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 6.93 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 2H), 2.63 (t, 2H), 2.63 (s, 3H), 2.13 (d, 2H); Mass: 412 109109 1H NMR (300 MHz, CDCl3) δ 7.90 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.43 (d, 1H, J = 8.2 Hz), 6.20 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.80 (d, 2H), 3.29 (s, 3H), 2.92 (t, 2H), 2.58 (s, 3H), 2.56 (t, 2H), 2.24 (m, 2H) ; Mass : 463.5 1 H NMR (300 MHz, CDCl 3) δ 7.90 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.43 (d, 1H, J = 8.2 Hz), 6.20 (m, 1H), 6.06 2H), 2.24 (s, 3H), 2.92 (t, 2H), 2.58 (s, 3H) m, 2H); Mass: 463.5 110110 1H NMR (300 MHz, CDCl3) δ 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 6.93 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.56 (d, 2H), 2.83 (t, 2H), 2.46 (t, 2H), 2.20 (s, 3H), 2.08 (m, 2H) ; Mass : 412 1 H NMR (300 MHz, CDCl 3) δ 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 6.93 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 2H), 2.63 (t, 2H), 2.63 (s, 3H), 2.13 (d, 2H); Mass: 412 111111 1H NMR (300 MHz, CDCl3) δ 7.65 (s, 2H), 7.61 (d, 1H, J = 8.4 Hz), 7.33 (d, 1H, J = 8.4 Hz), 6.14 (m, 1H), 5.95 (m, 1H), 5.14 (d, 2H), 4.55 (d, 2H), 2.90 (t, 2H), 2.56 (t, 2H), 2.54 (s, 3H), 2.21 (m, 2H) ; Mass : 430.5 1 H NMR (300 MHz, CDCl 3) δ 7.65 (s, 2H), 7.61 (d, 1H, J = 8.4 Hz), 7.33 (d, 1H, J = 8.4 Hz), 6.14 (m, 1H), 5.95 2H), 2.54 (s, 3H), 2.21 (m, 2H), 5.14 (d, 2H), 4.55 (d, 2H), 2.90 (t, 2H). Mass: 430.5 113113 1H NMR (300 MHz, CDCl3) δ 7.73 (d, 1H, J = 8.4 Hz), 7.72 (s, 2H), 6.97 (d, 1H, J = 8.4 Hz), 5.92 (s, 2H), 5.29 (s, 2H), 2.83 (t, 2H), 2.45 (t, 2H), 2.23 (s, 3H), 2.08 (m, 2H) ; Mass : 402 1 H NMR (300 MHz, CDCl 3) δ 7.73 (d, 1H, J = 8.4 Hz), 7.72 (s, 2H), 6.97 (d, 1H, J = 8.4 Hz), 5.92 (s, 2H), 5.29 (s, 2H), 2.83 (t, 2H), 2.45 (t, 2H), 2.23 (s, 3H), 2.08 (m, 2H); Mass: 402 114114 1H NMR (300 MHz, CDCl3) δ 7.88 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 7.02 (d, 1H, J = 8.4 Hz), 6.16 (m, 1H), 6.04 (m, 1H), 5.27 (d, 2H), 4.82 (d, 2H), 3.28 (s, 3H), 2.84 (t, 2H), 2.47 (t, 2H), 2.27 (s, 3H), 2.09 (m, 2H) ; Mass : 445 1 H NMR (300 MHz, CDCl 3) δ 7.88 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 7.02 (d, 1H, J = 8.4 Hz), 6.16 (m, 1H), 6.04 2H), 2.27 (s, 3H), 2.09 (m, 2H), 5.27 (d, 2H) m, 2H); Mass: 445 115115 1H NMR (300 MHz, CDCl3) δ 7.90 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.43 (d, 1H, J = 8.2 Hz), 6.20 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.80 (d, 2H), 3.29 (s, 3H), 2.92 (t, 2H), 2.58 (s, 3H), 2.56 (t, 2H), 2.24 (m, 2H) ; Mass : 463.5 1 H NMR (300 MHz, CDCl 3) δ 7.90 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.43 (d, 1H, J = 8.2 Hz), 6.20 (m, 1H), 6.06 2H), 2.24 (s, 3H), 2.92 (t, 2H), 2.58 (s, 3H) m, 2H); Mass: 463.5 116116 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 7.7 Hz, 1H), 7.78 (d, J = 7.7 Hz, 2H), 7.32 (d, J = 7.8 Hz, 1H), 4.91 (t, 2H), 4.66 (t, 2H), 3.09 (s, 3H), 2.52-1.99 (m, 6H) 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 7.7 Hz, 1H), 7.78 (d, J = 7.7 Hz, 2H), 7.32 (d, J = 7.8 Hz, 1H), 4.91 (t , 2H), 4.66 (t, 2H), 3.09 (s, 3H), 2.52 - 117117 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.0 Hz, 1H), 7.68 (S, 2H), 7.31 (d, J = 8.4 Hz, 1H), 4.96 (t, 2H), 4.66 (t, 2H), 3.21 (s, 3H), 2.50-1.98 (m, 6H) 1 H NMR (300 MHz, CDCl 3) δ 7.92 (d, J = 8.0 Hz, 1H), 7.68 (S, 2H), 7.31 (d, J = 8.4 Hz, 1H), 4.96 (t, 2H), 4.66 (t, 2H), 3.21 (s, 3H), 2.50 - 1.98 (m, 6H) 118118 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.30 (d, J = 8.1 Hz, 1H), 4.74 (t, J = 7.1 Hz, 2H), 4.31 (t, J = 6.0 Hz, 2H), 3.26 (s, 3H), 2.61-1.95 (m, 8H) 1 H NMR (300 MHz, CDCl 3) δ 7.94 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.30 (d, J = 8.1 Hz, 1H), 4.74 (t, J = 7.1 Hz , 2H), 4.31 (t, J = 6.0 Hz, 2H), 3.26 (s, 3H), 2.61-1.95 (m, 8H) 119119 1H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.63-7.60 (m, 3H), 4.76 (t, 2H), 4.32 (t, 2H), 3.28 (s, 3H), 2.59-2.56 (m, 8H) 1 H NMR (500 MHz, CDCl 3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.63-7.60 (m, 3H), 4.76 (t, 2H), 4.32 (t, 2H), 3.28 (s, 3H), 2.59-2.56 (m, 8H) 120120 1H NMR (300 MHz, CDCl3) δ 7.70 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 6.92 (d, 1H, J = 8.4 Hz), 4.66 (t, 2H), 4.13 (t, 2H), 4.08 (t, 2H), 3.79 (t, 2H), 2.84 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H) ; Mass : 430 1 H NMR (300 MHz, CDCl 3) δ 7.70 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 6.92 (d, 1H, J = 8.4 Hz), 4.66 (t, 2H), 4.13 2H), 4.08 (t, 2H), 3.79 (t, 2H), 2.84 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H); Mass: 430 121121 1H NMR (300 MHz, CDCl3) δ 7.60 (s, 2H), 7.57 (d, 1H, J = 8.3 Hz), 7.28 (d, 1H, J = 8.2 Hz), 4.64 (t, 2H), 4.07 (t, 2H), 4.06 (t, 2H), 3.76 (t, 2H), 2.74 (t, 2H), 2.51 (t, 2H), 2.40 (s, 3H), 2.15 (m, 2H), 2.06 (s, 3H) ; Mass : 472 1 H NMR (300 MHz, CDCl 3) δ 7.60 (s, 2H), 7.57 (d, 1H, J = 8.3 Hz), 7.28 (d, 1H, J = 8.2 Hz), 4.64 (t, 2H), 4.07 2H), 4.06 (t, 2H), 3.76 (t, 2H), 2.74 (t, 2H), 2.51 (t, 2H), 2.40 s, 3H); Mass: 472 122122 1H NMR (300 MHz, CDCl3) δ 7.61 (s, 2H), 7.58 (d, 1H, J = 8.3 Hz), 7.30 (d, 1H, J = 8.2 Hz), 4.64 (t, 2H), 4.09 (t, 2H), 4.06 (t, 2H), 3.76 (t, 2H), 2.87 (t, 2H), 2.55 (t, 2H), 2.49 (s, 3H), 2.20 (m, 2H) ; Mass : 448.5 1 H NMR (300 MHz, CDCl 3) δ 7.61 (s, 2H), 7.58 (d, 1H, J = 8.3 Hz), 7.30 (d, 1H, J = 8.2 Hz), 4.64 (t, 2H), 4.09 (t, 2H), 4.06 (t, 2H), 3.76 (t, 2H), 2.87 (t, 2H), 2.55 (t, 2H), 2.49 (s, 3H), 2.20 Mass: 448.5 123123 1H NMR (300 MHz, CDCl3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.98 (d, 1H, J = 8.4 Hz), 4.69 (t, 2H), 4.20 (t, 2H), 4.12 (t, 2H), 3.84 (t, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H) ; Mass : 463 1 H NMR (300 MHz, CDCl 3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.98 (d, 1H, J = 8.4 Hz), 4.69 (t, 2H), 4.20 2H), 3.18 (t, 2H), 3.84 (t, 2H), 3.26 (s, 3H), 2.83 m, 2H); Mass: 463 124124 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 7.38 (d, 1H, J = 8.4 Hz), 4.70 (t, 2H), 4.17 (t, 2H), 4.12 (t, 2H), 3.86 (t, 2H), 3.26 (s, 3H), 2.90 (t, 2H), 2.55 (t, 2H), 2.50 (s, 3H), 2.21 (m, 2H) ; Mass : 481.5 1 H NMR (300 MHz, CDCl 3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 7.38 (d, 1H, J = 8.4 Hz), 4.70 (t, 2H), 4.17 2H), 2.50 (s, 3H), 2.21 (t, 2H), 4.12 (t, 2H), 3.86 (t, 2H), 3.26 (s, m, 2H); Mass: 481.5 125125 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 7.38 (d, 1H, J = 8.4 Hz), 4.70 (t, 2H), 4.17 (t, 2H), 4.12 (t, 2H), 3.86 (t, 2H), 3.26 (s, 3H), 2.90 (t, 2H), 2.55 (t, 2H), 2.50 (s, 3H), 2.21 (m, 2H) ; Mass : 481.5 1 H NMR (300 MHz, CDCl 3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 7.38 (d, 1H, J = 8.4 Hz), 4.70 (t, 2H), 4.17 2H), 2.50 (s, 3H), 2.21 (t, 2H), 4.12 (t, 2H), 3.86 (t, 2H), 3.26 (s, m, 2H); Mass: 481.5 126126 1H NMR (300 MHz, CDCl3) δ 7.69 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.94 (d, 1H, J = 8.4 Hz), 5.08 (s, 2H), 4.69 (t, 2H), 4.28 (t, 2H), 2.83 (t, 2H), 2.45 (t, 2H), 2.17 (s, 3H), 2.08 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.69 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.94 (d, 1H, J = 8.4 Hz), 5.08 (s, 2H), 4.69 2H), 2.18 (s, 3H), 2.08 (m, 2H), 4.28 (t, 2H) 127127 1H NMR (300 MHz, CDCl3) δ 7.62 (s, 2H), 7.58 (d, 1H, J = 8.4 Hz), 7.32 (d, 1H, J = 8.4 Hz), 5.02 (s, 2H), 4.66 (t, 2H), 4.25 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.40 (s, 3H), 2.15 (m, 2H), 2.09 (s, 3H) 1 H NMR (300 MHz, CDCl 3) δ 7.62 (s, 2H), 7.58 (d, 1H, J = 8.4 Hz), 7.32 (d, 1H, J = 8.4 Hz), 5.02 (s, 2H), 4.66 2H), 2.05 (t, 2H), 4.25 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H) 128128 1H NMR (300 MHz, CDCl3) δ 7.62 (s, 2H), 7.59 (d, 1H, J = 8.4 Hz), 7.33 (d, 1H, J = 8.4 Hz), 5.03 (s, 2H), 4.67 (t, 2H), 4.25 (t, 2H), 2.88 (t, 2H), 2.54 (t, 2H), 2.48 (s, 3H), 2.19 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.62 (s, 2H), 7.59 (d, 1H, J = 8.4 Hz), 7.33 (d, 1H, J = 8.4 Hz), 5.03 (s, 2H), 4.67 2H), 2.48 (s, 3H), 2.19 (m, 2H), 2.48 (t, 2H) 129129 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 7.00 (d, 1H, J = 8.4 Hz), 5.19 (s, 2H), 4.74 (t, 2H), 4.38 (t, 2H), 3.24 (s, 3H), 2.83 (t, 2H), 2.45 (t, 2H), 2.17 (s, 3H), 2.09 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 7.00 (d, 1H, J = 8.4 Hz), 5.19 (s, 2H), 4.74 2H), 2.18 (s, 3H), 2.09 (m, 2H), 2.38 (s, 3H) 130130 1H NMR (300 MHz, CDCl3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 7.35 (d, 1H, J = 8.4 Hz), 5.15 (s, 2H), 4.74 (t, 2H), 4.40 (t, 2H), 3.22 (s, 3H), 2.76 (t, 2H), 2.52 (t, 2H), 2.39 (s, 3H), 2.17 (m, 2H), 2.09 (s, 3H) 1 H NMR (300 MHz, CDCl 3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 7.35 (d, 1H, J = 8.4 Hz), 5.15 (s, 2H), 4.74 2H), 4.40 (t, 2H), 3.22 (s, 3H), 2.76 (t, 2H), 2.52 (t, 2H), 2.39 s, 3H) 131131 1H NMR (500 MHz, CDCl3) δ 7.88 (d, J = 8.0 Hz, 1H), 7.65-7.69 (m, 2H), 7.03 (d, J = 8.0 Hz, 1H), 5.80 (s, 3H), 5.36 (s, 3H), 3.34 (s, 3H), 2.84 (t, J = 6.4 Hz, 2H), 2.46 (t, J = 6.4 Hz, 2H), 2.32 (s, 3H), 2.06-2.13 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.88 (d, J = 8.0 Hz, 1H), 7.65-7.69 (m, 2H), 7.03 (d, J = 8.0 Hz, 1H), 5.80 (s, 3H) , 5.36 (s, 3H), 3.34 (s, 3H), 2.84 (t, J = 6.4 Hz, 2H), 2.46 (t, J = 6.4 Hz, 2H), 2.32 (s, 3H), 2.06-2.13 ( m, 2H) 132132 1H NMR (500 MHz, CDCl3) δ 7.87 (d, J = 8.3 Hz, 1H), 7.62-7.69 (m, 2H), 7.00 (d, J = 8.3 Hz, 1H), 4.72 (t, J = 6.7 Hz, 2H), 4.22 (t, J = 6.7 Hz, 2H), 3.29 (s, 3H), 3.22 (t, J = 6.7 Hz, 2H), 2.97 (t, J = 6.7 Hz, 2H), 2.84 (t, J = 6.3 Hz, 2H), 2.47 (t, J = 6.7 Hz, 2H), 2.24 (s, 3H), 2.06-2.13 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.87 (d, J = 8.3 Hz, 1H), 7.62-7.69 (m, 2H), 7.00 (d, J = 8.3 Hz, 1H), 4.72 (t, J = 6.7 Hz, 2H), 4.22 ( t, J = 6.7 Hz, 2H), 3.29 (s, 3H), 3.22 (t, J = 6.7 Hz, 2H), 2.97 (t, J = 6.7 Hz, 2H), 2.84 (t, J = 6.3 Hz, 2H), 2.47 (t, J = 6.7 Hz, 2H), 2.24 (s, 3H), 2.06-2.13 (m, 2H) 133133 1H NMR (300 MHz, CDCl3) δ 8.02 (s, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.84 (s, 1H), 7.43 (d, J = 8.1 Hz, 1 Hz), 7.05 (dt, J = 5.7, 48.6 Hz, 1H), 4.81-4.74 (m, 2H), 3.07 (s, 3H), 2.90 (t, J = 6.2 Hz, 2H), 2.56 (s, 3H), 2.54 (t, J = 7.0 Hz, 2H), 2.24- 2.16 (m, 2H) 1 H NMR (300 MHz, CDCl 3) δ 8.02 (s, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.84 (s, 1H), 7.43 (d, J = 8.1 Hz, 1 Hz), 7.05 (dt, J = 5.7, 48.6 Hz, 1H), 4.81-4.74 (m, 2H), 3.07 (s, 3H), 2.90 (t, J = 6.2 Hz, 2H), 2.56 (s, 3H), 2.54 (t, J = 7.0 Hz, 2H), 2.24-2.16 (m, 2H) 134134 1H NMR (500 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz, 1H), 7.80 (s, 2H), 7.02 (d J = 7.9, 1H), 6.98 (dt, J = 5.6, 69.0 Hz, 1H), 4.86-4.82 (m, 2H), 3.19 (s, 3H), 3.16-3.11 (m, 2H), 2.24 (s, 3H), 2.09-2.05 (m, 2H), 1.38 (t, J = 7.0 Hz, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.84 (d, J = 8.0 Hz, 1H), 7.80 (s, 2H), 7.02 (d J = 7.9, 1H), 6.98 (dt, J = 5.6, 69.0 Hz , 1H), 4.86-4.82 (m, 2H), 3.19 (s, 3H), 3.16-3.11 (m, 2H), 2.24 (s, 3H), 2.09-2.05 (m, 2H), 1.38 (t, J = 7.0 Hz, 2H) 135135 1H NMR (500 MHz, CDCl3) δ 7.85 (d, J = 8.0 Hz, 1H), 7.80 (s, 2H), 7.02 (d, J = 7.5 Hz, 1H), 6.96 (dt, J = 6.4, 51 Hz, 1H), 4.86-4.82 (m, 2H), 3.19 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.44 (t, J = 6.7 Hz, 2H), 2.25 (s, 3H), 2.10-2.05 (m, 2H) 1 H NMR (500 MHz, CDCl 3) δ 7.85 (d, J = 8.0 Hz, 1H), 7.80 (s, 2H), 7.02 (d, J = 7.5 Hz, 1H), 6.96 (dt, J = 6.4, 51 Hz, 1H), 4.86-4.82 ( m, 2H), 3.19 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.44 (t, J = 6.7 Hz, 2H), 2.25 (s, 3H), < / RTI > 2.10-2.05 (m, 2H) 136136 1H NMR (500 MHz, CDCl3) δ 7.84 (d, J = 7.9 Hz, 1H), 7.81 (s, 2H), 7.40 (d, J = 7.9 Hz, 1H), 6.96 (dt, J = 6.1, 50.4 Hz, 1H), 4.85-4.81 (m, 2H), 3.19 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.51 (t, J = 6.4 Hz, 2H), 2.49 (s, 3H), 2.18-2.13 (m, 2H), 2.10 (s, 3H) 1 H NMR (500 MHz, CDCl 3) δ 7.84 (d, J = 7.9 Hz, 1H), 7.81 (s, 2H), 7.40 (d, J = 7.9 Hz, 1H), 6.96 (dt, J = 6.1, 50.4 Hz, 1H), 4.85-4.81 ( m, 2H), 3.19 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.51 (t, J = 6.4 Hz, 2H), 2.49 (s, 3H), 2.18-2.13 (m, 2H), 2.10 (s, 3H)

상기 표 1에서 구체화된 화합물들의 대표적인 합성방법을 예시하면 하기와 같다.Representative synthesis methods of the compounds embodied in Table 1 are as follows.

실시예 1. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 2)의 합성
Example 1. Synthesis of 2- (3- (2- (2 H- 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3- Synthesis of Roxycyclohexy-2-en-1-one (Compound No. 2)

ⅰ)단계. 메틸 3-(2-브로모에톡시)-2,4-다이클로로벤조에이트I) step. Methyl 3- (2-bromoethoxy) -2,4-dichlorobenzoate

메틸 2,4-다이클로로-3-하이드록시벤조에이트 (90.48 mmol)를 아세톤 300 mL에 녹인 후, 1,2-다이브로모에탄 (452.4 mmol)과 탄산칼륨 (180.96 mmol)을 첨가하였다. 반응 혼합물을 60℃에서 6시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 에틸아세테이트, 물을 이용하여 추출하고 얻어진 유기층은 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 26 g (수율 88%)의 원하는 화합물을 얻을 수 있다. Dichloro-3-hydroxybenzoate (90.48 mmol) was dissolved in 300 mL of acetone, and then 1,2-dibromoethane (452.4 mmol) and potassium carbonate (180.96 mmol) were added. The reaction mixture was stirred at 60 DEG C for 6 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, and the solvent was removed. 26 g (88% yield) of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.55 (d, J = 8.5 Hz, 1H), 7.36 (d, J = 8.5 Hz, 1H), 4.33 (t, J = 6.8 Hz, 2H), 3.93 (s, 3H), 3.72 (t, J = 6.8 Hz, 2H)
1 H NMR (300 MHz, CDCl 3) δ 7.55 (d, J = 8.5 Hz, 1H), 7.36 (d, J = 8.5 Hz, 1H), 4.33 (t, J = 6.8 Hz, 2H), 3.93 (s , 3H), 3.72 (t, J = 6.8 Hz, 2H)

ⅱ)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2,4-다이클로로벤조에이트Ii) Step. Methyl 3- (2- (2 H- 1,2,3- triazol-2-yl) ethoxy) -2,4-chlorobenzoate

상기에서 얻어진 메틸 3-(2-브로모에톡시)-2,4-다이클로로벤조에이트 (18 mmol)를 아세토나이트릴 90 mL에 녹인 후, 1H-1,2,3-트리아졸 (26 mmol), 탄산칼륨 (37 mmol), 테트라부틸암모늄 브롬화물 촉매량을 첨가하였다. 반응 혼합물을 85℃에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 에틸아세테이트, 물을 이용하여 추출하고 얻어진 유기층은 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 2.34 g (수율 42%)의 원하는 화합물을 얻을 수 있다. The obtained methyl 3- (2-bromoethoxy) -2,4-dichlorobenzoate (18 mmol) was dissolved in acetonitrile (90 mL), and then 1 H- 1,2,3-triazole ), Potassium carbonate (37 mmol) and tetrabutylammonium bromide catalyst were added. The reaction mixture was stirred at 85 캜 for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, and the solvent was removed. 2.34 g (42% yield) of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.66 (s, 2H), 7.35 (d, J = 8.5 Hz, 1H), 7.32 (d, J = 8.5 Hz, 1H), 4.92 (t, J = 6.0 Hz, 2H), 4.51 (t, J = 6.0 Hz, 2H), 3.92 (s, 3H)
 1 H NMR (300 MHz, CDCl 3) δ 7.66 (s, 2H), 7.35 (d, J = 8.5 Hz, 1H), 7.32 (d, J = 8.5 Hz, 1H), 4.92 (t, J = 6.0 Hz , 2H), 4.51 (t, J = 6.0 Hz, 2H), 3.92 (s, 3H)

ⅲ)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸싸이오)벤조에이트Iii) step. Methyl 3- (2- (2 H- 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylthio) benzoate

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2,4-다이클로로벤조에이트 (100 mmol)를 N,N-다이메틸포름아마이드 300 mL에 녹인 후, 나트륨싸이오메톡사이드 (130 mmol)를 첨가하였다. 반응 혼합물을 50℃에서 6시간 동안 교반시키고, 반응이 종결되면, 에틸아세테이트로 희석하였다. 유기층은 포화 소금물로 3번 세척한 후에 1N 염화수소 수용액으로 1번 세척하고, 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 22.6 g (수율 69%)의 원하는 화합물을 얻을 수 있다.Methyl 3 obtained in the above (a 2- (2 H- 1,2,3- triazol-2-yl) ethoxy) -2,4-chlorobenzoate (100 mmol) of N, N- dimethylformamide Amide (300 mL), and sodium thiomethoxide (130 mmol) was added. The reaction mixture was stirred at 50 < 0 > C for 6 hours, and when the reaction was complete, it was diluted with ethyl acetate. The organic layer was washed three times with saturated brine, then washed once with 1N aqueous hydrochloric acid solution, dried over anhydrous magnesium sulfate, and the solvent was removed. 22.6 g (yield 69%) of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.66 (s, 2H), 7.60 (d, J = 8.5 Hz, 1H), 6.99(d, J = 8.5 Hz, 1H), 4.90 (t, J = 5.7 Hz, 2H), 4.49 (t, J = 5.7 Hz, 2H), 3.90 (s, 3H), 2.39 (s, 3H)
 1 H NMR (300 MHz, CDCl 3) δ 7.66 (s, 2H), 7.60 (d, J = 8.5 Hz, 1H), 6.99 (d, J = 8.5 Hz, 1H), 4.90 (t, J = 5.7 Hz , 2H), 4.49 (t, J = 5.7 Hz, 2H), 3.90 (s, 3H), 2.39 (s, 3H)

ⅳ)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트Iv) step. Methyl 3- (2- (2 H- 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoate

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸싸이오)벤조에이트 (30 mmol)를 테트라하이드로퓨란 90 mL, 메탄올 90 mL, 물 180 mL에 녹인 후, 옥손 (66 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면, 감압 하에서 용매를 농축시켰다. 반응 혼합물을 에틸아세테이트로 희석하고, 염화나트륨 수용액으로 세척한 다음, 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 7.0 g (수율 65%)의 원하는 화합물을 얻을 수 있다.Obtained in the above-mentioned methyl 3- (2- (2 H- 1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylthio) benzoate (30 mmol) of tetrahydro- After dissolving in 90 mL of furan, 90 mL of methanol and 180 mL of water, Oxone (66 mmol) was added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was diluted with ethyl acetate, washed with aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and the solvent removed. 7.0 g (65% yield) of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 8.2 Hz, 1H), 4.99 (t, J = 5.0 Hz, 2H), 4.74 (t, J = 5.0 Hz, 2H), 3.97 (s, 3H), 3.22 (s, 3H)
1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 8.2 Hz, 1H), 4.99 (t, J = 5.0 Hz, 2H), 4.74 (t , J = 5.0 Hz, 2H) , 3.97 (s, 3H), 3.22 (s, 3H)

ⅴ)단계. 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조산 V) step. (2- (2 H- 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoic acid

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (10 mmol)를 테트라하이드로퓨란 30 mL, 물 30 mL에 녹인 후, 수산화나트륨 (15 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면, 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 얻어진 화합물 3.0 g (수율 95%)은 추가적인 정제 과정을 거치지 않고 다음 단계에 이용할 수 있다. (10 mmol) of methyl 3- (2- (2 H- 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoate 30 mL of furan and 30 mL of water, and then sodium hydroxide (15 mmol) was added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and the mixture was acidified and then extracted three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. 3.0 g (95% yield) of the compound obtained can be used in the next step without further purification.

1H NMR (300 MHz, CDCl3) δ 7.84 (d, J = 8.1 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 4.95 (t, J = 5.0 Hz, 2H), 4.58 (t, J = 5.0 Hz, 2H), 3.26 (s, 3H)
 1 H NMR (300 MHz, CDCl 3) δ 7.84 (d, J = 8.1 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 4.95 (t, J = 5.0 Hz, 2H), 4.58 (t , J = 5.0 Hz, 2H), 3.26 (s, 3H)

ⅵ)단계. 3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 Vi) Step. 3-oxo-cyclohexyl-1-Line-1-yl (ethoxy-2- (2 H- 1,2,3- triazol-2-yl)) -2-chloro-4- (methylsulfonyl) 3- Benzoate

상기에서 얻어진 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조산 (1.53 mmol)을 테트라하이드로퓨란 8 mL에 녹인 후, 2-클로로-1-메틸피리디움 요오드화물 (1.99 mmol), 1,3-사이클로헥사다이온 (1.84 mmol), 트리에틸아민 (4.13 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 반응 혼합물을 에틸아세테이트로 희석하고, 염화암모늄 수용액으로 2번 세척한 후에 1N 염화수소 수용액으로 1번 세척한 다음, 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.38 g (수율 61%)의 원하는 화합물을 얻을 수 있다.The (ethoxy-2- (2 H- 1,2,3- triazol-2-yl)) -2-chloro-4- (methylsulfonyl) benzoic acid (1.53 mmol) 3- obtained above in tetrahydrofuran 8 mL, and then 2-chloro-1-methylpyridinium iodide (1.99 mmol), 1,3-cyclohexadazole (1.84 mmol) and triethylamine (4.13 mmol) were added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was diluted with ethyl acetate, washed twice with aqueous ammonium chloride solution, washed once with 1N aqueous hydrochloric acid solution, dried over anhydrous magnesium sulfate, and the solvent was removed. 0.38 g (61% yield) of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 6.04 (s, 1H), 4.97 (t, J = 4.8 Hz, 2H), 4.72 (t, J = 4.9 Hz, 2H), 3.21 (s, 3H), 2.66 (t, J = 6.2 Hz, 2H), 2.46 (t, J = 6.2 Hz, 2H), 2.13 (quin, J = 6.4 Hz, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 6.04 (s, 1H), 4.97 (t, J = 4.8 Hz, 2H), 4.72 (t, J = 4.9 Hz, 2H), 3.21 (s, 3H), 2.66 (t, J = 6.2 Hz, 2H), 2.46 (t, J = 6.2 Hz , 2H), 2.13 (quin, J = 6.4 Hz, 2H)

ⅶ)단계. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 Ⅶ) Step. 2- (3- (2- (2 H- 1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-Sen-1-one

상기에서 얻어진 3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (1.47 mmol)를 아세토나이트릴 7 mL에 녹인 후, 아세톤 시아노하이드린 3방울, 트리에틸아민 (2.50 mmol), 시안화칼륨 (2.21 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.50 g (수율 84%)의 원하는 화합물을 얻을 수 있다.The obtained 3- oxocyclohex-1-en-1-yl 3- (2- (2 H- 1,2,3-triazol-2-yl) ethoxy) Sulfonyl) benzoate (1.47 mmol) was dissolved in acetonitrile (7 mL), and then three drops of acetone cyanohydrin, triethylamine (2.50 mmol) and potassium cyanide (2.21 mmol) were added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and acid treated and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography afforded 0.50 g (84% yield) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz, 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81-2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H)
 1 H NMR (500 MHz, CDCl 3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz , 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81-2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H)

실시예 2. 2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 4)의 합성Example 2. 2- (3- (4- (2 H- 1,2,3- triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy Synthesis of Roxycyclohexy-2-en-1-one (Compound No. 4)

3-옥소사이클로헥-1-센-1-일 3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (0.58 mmol)를 아세토나이트릴 3 mL에 녹인 후, 아세톤 시아노하이드린 2 방울, 트리에틸아민 (0.99 mmol), 시안화칼륨 (0.87 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.20 g (수율 73%)의 원하는 화합물을 얻을 수 있다.3-oxo-cyclohexyl-1-sen-yl 3- (4- (2 H- 1,2,3- triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) Benzoate (0.58 mmol) was dissolved in acetonitrile (3 mL), and then 2 drops of acetone cyanohydrin, triethylamine (0.99 mmol) and potassium cyanide (0.87 mmol) were added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and acid treated and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography afforded 0.20 g (73% yield) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 7.5 Hz, 1H), 7.63 (s, 2H), 7.09 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 6.8 Hz, 2H), 4.30 (t, J = 6.2 Hz, 2H), 3.27 (s, 3H), 2.83 (t, 2H), 2.47 (t, 2H), 2.24 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 1.94-1.90 (m, 2H)
 1 H NMR (500 MHz, CDCl 3) δ 7.95 (d, J = 7.5 Hz, 1H), 7.63 (s, 2H), 7.09 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 6.8 Hz , 2H), 4.30 (t, J = 6.2 Hz, 2H), 3.27 (s, 3H), 2.83 (t, 2H), 2.47 (t, 2H), 2.24 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 1.94-1.90 (m, 2H)

실시예 3. 2-(3-(4-(1H-1,2,3-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 9)의 합성Example 3. Preparation of 2- (3- (4- (1H - 1,2,3-triazol - 1-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) Synthesis of Roxycyclohexy-2-en-1-one (Compound No. 9)

3-옥소사이클로헥-1-센-1-일 3-(4-(1H-1,2,3-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (0.63 mmol)를 아세토나이트릴 3 mL에 녹인 후, 아세톤 시아노하이드린 2방울, 트리에틸아민 (1.07 mmol), 시안화칼륨 (0.95 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.22 g (수율 73%)의 원하는 화합물을 얻을 수 있다.3-oxo-cyclohexyl-1-sen-yl 3- (4- (1 H- 1,2,3- triazol-1-yl) butoxy) -2-chloro-4- (methylsulfonyl) Benzoate (0.63 mmol) was dissolved in acetonitrile (3 mL), and then 2 drops of acetone cyanohydrin, triethylamine (1.07 mmol) and potassium cyanide (0.95 mmol) were added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and acid treated and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography afforded 0.22 g (73% yield) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 8.1 Hz, 1H), 7.76 (s, 1H), 7.64 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 4.54 (t, J = 7.5 Hz, 2H), 4.30 (t, J = 6.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.0 HZ, 2H), 2.47 (t, J = 7.5 Hz, 2H), 2.22 (t, J = 6.5 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.97-1.93 (m, 2H)
 1 H NMR (500 MHz, CDCl 3) δ 7.96 (d, J = 8.1 Hz, 1H), 7.76 (s, 1H), 7.64 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 4.54 (t, J = 7.5 Hz, 2H), 4.30 (t, J = 6.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.0 HZ, 2H), 2.47 (t, J = 7.5 Hz 2H), 2.22 (t, J = 6.5 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.97-1.93

실시예 4. 2-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온(화합물번호 12)의 합성Example 4. Preparation of 2- (3- (2- (1H- 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) Synthesis of Roxycyclohexy-2-en-1-one (Compound No. 12)

3-옥소사이클로헥-1-센-1-일 3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (0.52 mmol)를 아세토나이트릴 3 mL에 녹인 후, 아세톤 시아노하이드린 2방울, 트리에틸아민 (0.88 mmol), 시안화칼륨 (0.78 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.17 g (수율 80%)의 원하는 화합물을 얻을 수 있다. 3-oxo-cyclohexyl-1-sen-yl 3- (2- (1 H- 1,2,4- triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) Benzoate (0.52 mmol) was dissolved in acetonitrile (3 mL), and then 2 drops of acetone cyanohydrin, triethylamine (0.88 mmol) and potassium cyanide (0.78 mmol) were added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and acid treated and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography afforded 0.17 g (80% yield) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04 (t, J = 6.5 Hz, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 t, J = 6.5 Hz, 2H)

실시예 5. 2-(3-(4-(1H-1,2,4-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 14)의 합성Example 5. Synthesis of 2- (3- (4- (1H - 1,2,4 - triazol-1 - yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) Synthesis of Roxycyclohexy-2-en-1-one (Compound No. 14)

3-옥소사이클로헥-1-센-1-일 3-(4-(1H-1,2,4-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (0.33 mmol)를 아세토나이트릴 2 mL에 녹인 후, 아세톤 시아노하이드린 1방울, 트리에틸아민 (0.57 mmol), 시안화칼륨 (0.50 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.11 g (수율 70%)의 원하는 화합물을 얻을 수 있다. 1 - yl) -3- (4- (1H-1,2,4 - triazol-1 - yl) butoxy) -2-chloro-4- (methylsulfonyl) Benzoate (0.33 mmol) was dissolved in acetonitrile (2 mL), and then one drop of acetone cyanohydrin, triethylamine (0.57 mmol) and potassium cyanide (0.50 mmol) were added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and acid treated and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography afforded 0.11 g (70% yield) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 8.18 (s, 1H), 8.00 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 4.34-4.29 (m, 4H), 3.26 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.19 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.95-1.91 (m, 2H)
 1 H NMR (500 MHz, CDCl 3) δ 8.18 (s, 1H), 8.00 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 4.34 J = 6.0 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.19 (t, J = 7.0 Hz, 2H) , 2.10 (t, J = 6.5 Hz, 2H), 1.95-1.91 (m, 2H)

실시예 6. 3-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 27)의 합성Example 6. Synthesis of 3- (3- (2- (1H - 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) Oxobicyclo [3.2.1] oct-3-en-2-one (Compound No. 27)

4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (1.60 mmol)를 아세토나이트릴 8 mL에 녹인 후, 아세톤 시아노하이드린 5방울, 트리에틸아민 (2.72 mmol), 시안화칼륨 (2.4 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.66 g (수율 92%)의 원하는 화합물을 얻을 수 있다.Oxo bicyclo [3.2.1] oct-2-yl-2-yl 3- (2- (1 H- 1,2,4- triazol- 1- yl) ethoxy) (Methylsulfonyl) benzoate (1.60 mmol) was dissolved in acetonitrile (8 mL), and then 5 drops of acetone cyanohydrin, triethylamine (2.72 mmol) and potassium cyanide (2.4 mmol) were added. The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and acid treated and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. 0.66 g (92% yield) of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42-3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42-3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H) , 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H)

실시예 7. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 41)의 합성
Example 7. Preparation of 2- (3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) Synthesis of Roxycyclohexy-2-en-1-one (Compound No. 41)

i) 단계. 메틸-3-하이드록시-2-메틸-4-나이트로벤조에이트i) step. Methyl-3-hydroxy-2-methyl-4-nitrobenzoate

메틸 3-하이드록시-2-메틸벤조에이트 (50 g, 0.301 mole)을 에틸아세테이트 50 mL과 아세트산 200 mL에 녹이고, 질산 (24.4 mL, 0.331 mmol)을 10분에 걸쳐서 천천히 적가하고, 상온에서 1시간 동안 교반하였다. 반응용액을 물 1 L에 희석하고 에틸 아세테이트로 추출하면서 물로 2회 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (다이클로로메탄/n-헥산 = 1/1) 로 정제하여 노란색 고체상태의 목적화합물 31 g (48% 수율)을 얻었다.(50 g, 0.301 mole) was dissolved in 50 mL of ethyl acetate and 200 mL of acetic acid, nitric acid (24.4 mL, 0.331 mmol) was slowly added dropwise over 10 minutes, and 1 Lt; / RTI > The reaction solution was diluted with 1 L of water and extracted twice with ethyl acetate and washed twice with water. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane / n -hexane = 1/1) to obtain 31 g (48% yield) of the desired compound in yellow solid state.

1H NMR (300 MHz, CDCl3) δ 11.08 (s, OH), 8.02 (d, 1H, J = 8.8 Hz), 7.36 (d, 1H, J = 8.8 Hz), 3.97 (s, 3H), 2.54 (s, 3H)
1 H NMR (300 MHz, CDCl 3) δ 11.08 (s, OH), 8.02 (d, 1H, J = 8.8 Hz), 7.36 (d, 1H, J = 8.8 Hz), 3.97 (s, 3H), 2.54 (s, 3 H)

ⅱ)단계. 메틸 3-(2-브로모에톡시)-2-메틸벤조에이트Ii) Step. Methyl 3- (2-bromoethoxy) -2-methylbenzoate

상기에서 얻어진 메틸-3-하이드록시-2-메틸-4-나이트로벤조에이트 (3.0 g, 14.21 mmol)을 다이메틸포름아마이드 30 mL에 녹이고 탄산칼륨 (5.9 g, 42.6 mmol) 과 다이브로모에탄 (3.7 mL, 42.6 mmol)을 첨가한 후 60 ℃에서 3시간동안 교반하였다. 반응용액을 물로 희석시키고 에틸 아세테이트 150 mL로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 5/1)로 정제하여 무색 오일상태의 목적화합물 3.67 g (81% 수율)을 얻었다.The resulting methyl-3-hydroxy-2-methyl-4-nitrobenzoate (3.0 g, 14.21 mmol) was dissolved in 30 mL of dimethylformamide, and potassium carbonate (5.9 g, 42.6 mmol) and dibromoethane 3.7 mL, 42.6 mmol) was added thereto, followed by stirring at 60 ° C for 3 hours. The reaction solution was diluted with water and extracted with ethyl acetate (150 mL), washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 5/1) to obtain 3.67 g (81% yield) of the desired compound as a colorless oil.

1H NMR (300 MHz, CDCl3) : δ 7.72 (d, 1H, J = 8.8 Hz), 7.65 (d, 1H, J = 8.8 Hz), 4.31 (t, 2H), 3.95 (s, 3H), 3.70 (t, 2H), 2.60 (s, 3H) 1 H NMR (300 MHz, CDCl 3): δ 7.72 (d, 1H, J = 8.8 Hz), 7.65 (d, 1H, J = 8.8 Hz), 4.31 (t, 2H), 3.95 (s, 3H), 3.70 (t, 2 H), 2.60 (s, 3 H)

ⅲ)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-나이트로벤조에이트Iii) step. Methyl 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4-nitrobenzoate

상기에서 얻어진 메틸 3-(2-브로모에톡시)-2-메틸벤조에이트 3.0 g (9.43 mmol)을 N,N-다이메틸포름아마이드 30 mL에 녹이고 1H-1,2,3-트리아졸 (0.98 g, 14.14 mmol), 탄산칼륨 (3.91 g, 28.29 mmol) 그리고 테트라부틸암모늄 브롬화물 (0.3 g, 0.94 mmol)을 차례로 첨가한 후 60 ℃에서 3시간동안 교반하였다. 반응용액을 물로 희석시키고 에틸 아세테이트 150 mL로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 3/1) 로 정제하여 N-2 위치가 치환된 고체상태의 목적화합물 1.8 g (62% 수율)과 N-1 위치가 치환된 고체상태의 화합물 1.15 g (39% 수율)을 얻었다.3.0 g (9.43 mmol) of methyl 3- (2-bromoethoxy) -2-methylbenzoate obtained above was dissolved in 30 mL of N, N -dimethylformamide, and 1 H -1,2,3-triazole 0.98 g, 14.14 mmol), potassium carbonate (3.91 g, 28.29 mmol) and tetrabutylammonium bromide (0.3 g, 0.94 mmol) were successively added thereto, followed by stirring at 60 ° C for 3 hours. The reaction solution was diluted with water and extracted with ethyl acetate (150 mL), washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 3/1) to obtain 1.8 g (62% yield) of the desired compound in the form of solid at the N-2 position 1.15 g (39% yield) of the title compound.

N-2 위치가 치환된 화합물 : 1H NMR (300 MHz, CDCl3) δ 7.69 (d, 1H, J = 8.8 Hz), 7.68 (s, 2H), 7.63 (d, 1H, J = 8.8 Hz), 4.89 (t, 2H), 4.51 (s, 2H), 3.92 (s, 3H), 2.25 (s, 3H)The compounds substituted the N-2 position: 1 H NMR (300 MHz, CDCl 3) δ 7.69 (d, 1H, J = 8.8 Hz), 7.68 (s, 2H), 7.63 (d, 1H, J = 8.8 Hz) , 4.89 (t, 2H), 4.51 (s, 2H), 3.92 (s, 3H)

N-1 위치가 치환된 화합물 : 1H NMR (300 MHz, CDCl3) δ 7.76 (m, 2H), 7.71 (d, 1H, J = 8.8 Hz), 7.64 (d, 1H, J = 8.8 Hz), 4.84 (t, 2H), 4.42 (s, 2H), 3.92 (s, 3H), 2.22 (s, 3H)
N-1 position is substituted by the compound: 1 H NMR (300 MHz, CDCl 3) δ 7.76 (m, 2H), 7.71 (d, 1H, J = 8.8 Hz), 7.64 (d, 1H, J = 8.8 Hz) , 4.84 (t, 2H), 4.42 (s, 2H), 3.92 (s, 3H)

ⅳ)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸싸이오)벤조에이트Iv) step. Methyl 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylthio) benzoate

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-나이트로벤조에이트 1.65 g (5.39 mmol)을 N,N-다이메틸포름아마이드 25 mL에 녹이고 나트륨 싸이오메톡사이드 (0.76 g, 10.78 mmol)을 5분에 걸쳐 천천히 가해주고 상온에서 3시간동안 교반하였다. 반응용액을 물로 희석시키고 에틸 아세테이트 150 mL로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 3/1) 로 정제하여 고체상태의 목적화합물 1.36 g (82% 수율)을 얻었다.Of methyl 3- (2- (2 H -1,2,3- triazol-benzoate 1.65 g (5.39 mmol) in methyl-2-nitro-4-on-2-yl) obtained in the above-mentioned N, N - Sodium thiomethoxide (0.76 g, 10.78 mmol) was slowly added over 5 minutes and stirred at room temperature for 3 hours. The reaction solution was diluted with water and extracted with ethyl acetate (150 mL) The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 3/1) to obtain a solid state 1.36 g (82% yield) of the desired compound was obtained.

1H NMR (300 MHz, CDCl3) δ 7.67 (d, 1H, J = 8.4 Hz), 7.66 (s, 2H), 6.95 (d, 1H, J = 8.4 Hz), 4.88 (t, 2H), 4.33 (t, 2H), 3.84 (s, 3H), 2.39 (s, 3H), 2.30 (s, 3H)
1 H NMR (300 MHz, CDCl 3) δ 7.67 (d, 1H, J = 8.4 Hz), 7.66 (s, 2H), 6.95 (d, 1H, J = 8.4 Hz), 4.88 (t, 2H), 4.33 (t, 2H), 3.84 (s, 3H), 2.39 (s, 3H)

v) 단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조에이트v) step. Methyl 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoate

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸싸이오)벤조에이트 (1.36 g, 4.43 mmol)를 메탄올/테트라하이드로퓨란/물 (1/1/1)로 희석된 혼합용매 60 mL에 녹이고 옥손 10.8 g (17.72 mmol)을 가한 후 상온에서 16시간동안 교반하였다. 녹지 않는 고체는 에틸아세테이트로 세척하면서 여과하여 제거하고, 여액은 물로 희석시키고 에틸 아세테이트 150 mL로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 2/1) 로 정제하여 고체상태의 목적화합물 1.50 g (98% 수율)을 얻었다.Ethoxy-2-methyl-4- (methylthio) of methyl 3- (2- (2 H -1,2,3- triazol-2-yl) benzoate obtained in the step a (1.36 g, 4.43 mmol) Dissolved in 60 mL of a mixed solvent diluted with methanol / tetrahydrofuran / water (1/1/1), 10.8 g (17.72 mmol) of oxone was added, and the mixture was stirred at room temperature for 16 hours. The insoluble solid was washed with ethyl acetate The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by evaporation under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate = 2: 1), and the residue was purified by silica gel column chromatography ( N -hexane / ethyl acetate = 2/1) to obtain 1.50 g (98% yield) of the title compound as a solid.

1H NMR (300 MHz, CDCl3) δ 7.85 (d, 1H, J = 8.8 Hz), 7.73 (d, 1H, J = 8.8 Hz), 7.68 (s, 2H), 4.92 (t, 2H), 4.52 (t, 2H), 3.91 (s, 3H), 3.22 (s, 3H), 2.26 (s, 3H) 1 H NMR (300 MHz, CDCl 3) δ 7.85 (d, 1H, J = 8.8 Hz), 7.73 (d, 1H, J = 8.8 Hz), 7.68 (s, 2H), 4.92 (t, 2H), 4.52 (t, 2H), 3.91 (s, 3H), 3.22 (s, 3H), 2.26

ⅵ)단계. 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조산Vi) Step. 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl)

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조에이트 1.52 g (4.48 mmol)을 메탄올 20 mL과 테트라하이드로퓨란 10 mL에 녹이고 2N-NaOH (6.7 mL, 13.5 mmol)을 첨가한 후 상온에서 3시간동안 교반하였다. 반응이 완결되면 물로 희석하고 1N-HCl을 가하여 pH 3~4 정도의 산성용액이 되게 한 다음 에틸 아세테이트로 추출(100 mL x 2)하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 감압 하에 건조시켜 고체상태의 목적화합물 1.37 g (94% 수율)을 얻었다.1.52 g (4.48 mmol) of methyl 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy-2-methylsulfonyl) benzoate obtained in the above was dissolved in methanol After the reaction was completed, the reaction mixture was diluted with water, and 1N HCl was added thereto to adjust the pH to about 3 to 4. The reaction mixture was stirred at room temperature for 3 hours. The resulting organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by evaporation under reduced pressure. The obtained residue was dried under reduced pressure, and dried under reduced pressure. The residue was purified by silica gel column chromatography To give 1.37 g (94% yield) of the desired compound as a solid.

1H NMR (300 MHz, CDCl3) δ 7.90 (m, 2H), 7.70 (s, 2H), 4.95 (t, 2H), 4.55 (t, 2H), 3.25 (s, 3H), 2.32 (s, 3H)
1 H NMR (300 MHz, CDCl 3) δ 7.90 (m, 2H), 7.70 (s, 2H), 4.95 (t, 2H), 4.55 (t, 2H), 3.25 (s, 3H), 2.32 (s, 3H)

ⅶ)단계. 3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조에이트 Ⅶ) Step. 3-oxocyclohex-1-en-1-yl 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy- Eight

상기에서 얻어진 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조산 300 mg(0.92 mmol)을 다이클로로메탄 10 mL에 녹이고 옥살릴 클로라이드 (0.23 mL, 2.77 mmol) 을 첨가하고 DMF 2 방울을 가한 후 상온에서 1시간 동안 교반하였다. 이어서 반응용액을 감압 하에 농축시켜 용매를 제거하고 건조시켰다. 또 다른 반응용기에 사이클로헥사다이온 155 mg (1.38 mmol)을 취하여 다이클로로메탄 20 mL에 녹이고 트리에틸아민 (0.38 mL, 2.77 mmol)을 첨가하고 얼음물 수조를 이용하여 냉각 시켰다. 이어서 앞에서 얻은 acid chloride 화합물을 다이클로로메탄 10 mL에 녹여서 천천히 적가하고 상온에서 1시간 동안 교반하였다. 반응이 완결되면 반응용액을 물로 희석시키고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 1/1)로 정제하여 오일상태의 목적화합물 370 mg (95% 수율)을 얻었다.300 mg (0.92 mmol) of 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy-2- methyl-4- (methylsulfonyl) benzoic acid obtained above was dissolved in dichloromethane (0.23 mL, 2.77 mmol) was added to the reaction mixture, and 2 drops of DMF was added thereto, followed by stirring at room temperature for 1 hour. Then, the reaction solution was concentrated under reduced pressure to remove the solvent and dried. 155 mg (1.38 mmol) of cyclohexadazole was dissolved in 20 mL of dichloromethane, and triethylamine (0.38 mL, 2.77 mmol) was added and the mixture was cooled in an ice water bath. The acid chloride compound obtained above was dissolved in dichloromethane The reaction mixture was diluted with water, extracted with ethyl acetate (100 mL), and washed with water and brine. The extracted organic layer was washed with anhydrous sodium sulfate After drying, filtering and the solvent was removed by evaporation under reduced pressure and the resulting residue was purified by silica gel column chromatography. (N - hexane / ethyl acetate = 1/1) to give to give an oil (95% yield), 370 mg of the desired compound condition.

1H NMR (300 MHz, CDCl3) δ 7.92 (d, 1H, J = 8.4 Hz), 7.86 (d, 1H, J = 8.4 Hz), 7.70 (s, 2H), 6.03 (s, 1H), 4.94 (t, 2H), 4.55 (t, 2H), 3.25 (s, 3H), 2.66 (t, 2H), 2.48 (t, 2H), 2.30 (s, 3H), 2.14 (m, 2H)
1 H NMR (300 MHz, CDCl 3) δ 7.92 (d, 1H, J = 8.4 Hz), 7.86 (d, 1H, J = 8.4 Hz), 7.70 (s, 2H), 6.03 (s, 1H), 4.94 2H), 4.55 (t, 2H), 3.25 (s, 3H), 2.66 (t, 2H), 2.48

ⅷ)단계. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온Ⅷ) Step. 2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-Sen-1-one

상기에서 얻어진 3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조에이트 370 mg (0.883 mmol)을 아세토니트릴 20 mL에 녹이고 트리에틸아민 (0.18 mL, 1.32 mmol), 시안화칼륨 (57 mg, 0.88 mmol) 그리고 아세톤 시아노하이드린을 촉매량 (2 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 1N-HCl을 가하여 pH 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM) 로 정제하여 오일상태의 목적화합물 279 mg (75% 수율)을 얻었다.The resulting 3-oxocyclohex-1-en-1-yl 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy- (2-morpholinophenyl) benzoate (370 mg, 0.883 mmol) was dissolved in 20 mL of acetonitrile, and triethylamine (0.18 mL, 1.32 mmol), potassium cyanide (57 mg, 0.88 mmol) and acetone cyanohydrin After confirming the completion of the reaction by TLC, the reaction solution was diluted with water, acidified to pH 3 with 1N HCl, extracted with ethyl acetate (100 mL), washed with water The filtrate was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 279 mg (yield: 75% yield).

1H NMR (300 MHz, CDCl3) δ 7.83 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.97 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.80 (t, 2H), 2.43 (t, 2H), 2.06 (m, 2H), 2.06 (s, 3H)
 1 H NMR (300 MHz, CDCl 3) δ 7.83 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.97 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.56 2H), 2.06 (s, 3H), 2.80 (t, 2H)

실시예 8. (E)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 42)의 합성Example 8 Synthesis of ( E ) -2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) -4- (methylsulfonyl) benzoyl) -3-hydroxycyclohexy-2-en-1-one (Compound No. 42)

3-옥소사이클로헥-1-센-1-일 (E)-3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조에이트 (735 mg)를 아세토나이트릴에 녹인 후, 아세톤 시아노하이드린 (0.03 mL), 트리에틸아민 (0.44 mmol), 시안화칼륨 (154 mg)을 첨가하였다. 반응 혼합물을 상온에서 15시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 511 mg의 원하는 화합물을 얻을 수 있다. ( E ) -3 - ((4- (2 H -1,2,3-triazol-2-yl) (735 mg) was dissolved in acetonitrile, and acetone cyanohydrin (0.03 mL), triethylamine (0.44 mmol) and potassium cyanide (154 mg ). The reaction mixture was stirred at room temperature for 15 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and the mixture was acidified and then extracted three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. 511 mg of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.13-6.2 (m, 1H), 5.98-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.77 (d, J = 5.3 Hz, 1H), 3.25 (s, 3H), 2.75-2.88 (m, 2H), 2.38-2.52 (m, 2H), 2.00-2.14 (m, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.13-6.2 (m, 1H), 5.98-6.11 (m, 1H ), 5.14 (d, J = 5.6 Hz, 2H), 4.77 (d, J = 5.3 Hz, 1H), 3.25 (s, 3H), 2.75-2.88 (m, 2H ), 2.38-2.52 (m, 2H), 2.00-2.14 (m, 2H)

실시예 9. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 44)의 합성Example 9. Synthesis of 2- (3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoyl) -3-hydroxycyclohexyl 2-en-1-one (Compound No. 44)

3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조에이트 190 mg (0.49 mmol)을 아세토니트릴 10 mL에 녹이고 트리에틸아민 (0.09 mL), 시안화칼륨 (28 mg) 그리고 아세톤 시아노하이드린 (ACH)을 촉매량 (1 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 1N-HCl을 가하여 pH = 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM) 로 정제하여 목적화합물 157 mg (83% 수율)을 얻었다.3-oxocyclohex-1-en-1-yl 3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoate 190 (0.049 mL), potassium cyanide (28 mg) and acetone cyanohydrin (ACH) were added in a catalytic amount (1 drop), followed by stirring at room temperature for 8 hours . After confirming the completion of the reaction by TLC, the reaction solution was diluted with water, 1 N HCl was added to make an acidic solution of pH = 3, and the mixture was extracted with ethyl acetate (100 mL) and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 157 mg (83% yield) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.73 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.92 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.56 (t, 2H), 2.82 (t, 2H), 2.44 (t, 2H), 2.08 (m, 2H), 1.92 (s, 3H)
1 H NMR (300 MHz, CDCl 3) δ 7.73 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.92 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.56 2H), 2.82 (t, 2H), 2.44 (t, 2H), 2.08 (m,

실시예 10. (Z)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 45)의 합성Example 10 Synthesis of ( Z ) -2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) -4- (methylsulfonyl) benzoyl) -3-hydroxycyclohexy-2-en-1-one (Compound No. 45)

3-옥소사이클로헥-1-센-1-일 (Z)-3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조에이트 (508 mg)를 아세토나이트릴에 녹인 후, 아세톤 시아노하이드린 (0.02 mL), 트리에틸아민 (0.30 mmol), 시안화칼륨 (107 mg)을 첨가하였다. 반응 혼합물을 상온에서 15시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 345 mg의 원하는 화합물을 얻을 수 있다. ( Z ) -3 - ((4- (2 H -1,2,3-triazol-2-yl) (508 mg) was dissolved in acetonitrile, and then acetone cyanohydrin (0.02 mL), triethylamine (0.30 mmol) and potassium cyanide (107 mg ). The reaction mixture was stirred at room temperature for 15 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and the mixture was acidified and then extracted three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. 345 mg of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3)δ 7.97 (d, J = 8.1 Hz, 1H), 7.59-7.66 (m, 2H), 7.13 (d, J = 8.1 Hz, 1H), 6.14-6.25 (m, 1H), 6.00-6.11 (m, 1H), 5.29 (d, J = 6.7 Hz, 2H), 4.96 (d, J = 6.7 Hz, 2H), 3.30 (s, 3H), 2.84 (t, J = 6.2 Hz, 2H), 2.47 (t, J = 6.2Hz, 2H), 2.04-2.15 (m, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.97 (d, J = 8.1 Hz, 1H), 7.59-7.66 (m, 2H), 7.13 (d, J = 8.1 Hz, 1H), 6.14-6.25 (m, 1H), 6.00-6.11 (m, 1H ), 5.29 (d, J = 6.7 Hz, 2H), 4.96 (d, J = 6.7 Hz, 2H), 3.30 (s, 3H), 2.84 (t, J = 6.2 2H), 2.47 (t, J = 6.2 Hz, 2H), 2.04-2.15 (m, 2H)

실시예 11. 2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 48)의 합성Example 11. 2- (3 - ((4- (2 H -1,2,3- triazol-2-yl) -2-part tin-yl) oxy) -2-chloro-4- ( Methylsulfonyl) benzoyl) -3-hydroxycyclohexyl-2-en-1-one (Compound No. 48)

3-옥소사이클로헥-1-센-1-일 3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조에이트 (135 mg)를 아세토나이트릴에 녹인 후, 아세톤 시아노하이드린 (3 방울), 트리에틸아민 (0.08 mmol), 시안화칼륨 (29 mg)을 첨가하였다. 반응 혼합물을 상온에서 18시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 71 mg의 원하는 화합물을 얻을 수 있다.3-oxo-cyclohexyl-1-Line-1-yl 3 - ((4- (2 H -1,2,3- triazol-2-yl) -2-part tin-yl) oxy) -2 (3 drops), triethylamine (0.08 mmol), and potassium cyanide (29 mg) were added to the solution, which was dissolved in acetonitrile . The reaction mixture was stirred at room temperature for 18 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and the mixture was acidified and then extracted three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. 71 mg of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.63-7.70 (m, 2H), 7.12 (d, J = 8.0 Hz, 1H), 5.35 (s, 2H), 4.94 (s, 2H), 3.29 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.45 (t, J = 6.3 Hz, 2H), 2.08 (q, J = 6.1 Hz, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.63-7.70 (m, 2H), 7.12 (d, J = 8.0 Hz, 1H), 5.35 (s, 2H) J = 6.3 Hz, 2 H), 2.45 (t, J = 6.3 Hz, 2H), 2.08 (q, J = 6.1 Hz,

실시예 12. 2-(3-(((2H-1,2,3-트리아졸-2-일)메톡시)메톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 49)의 합성Example 12 2- (3 - ((2 H -1,2,3-triazol-2-yl) methoxy) methoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Hydroxycyclohex-2-en-1-one (Compound No. 49)

3-옥소사이클로헥-1-센-1-일 3-(((2H-1,2,3-트리아졸-2-일)메톡시)메톡시)-2-메틸-4-(메틸설포닐)벤조에이트 60 mg (0.138 mmol)을 아세토니트릴 6 mL에 녹이고 트리에틸아민 (0.028 mL, 0.21 mmol), 시안화칼륨 (9.0 mg, 0.138 mmol) 그리고 아세톤 시아노하이드린을 촉매량 (1 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물 (30 mL)로 희석시키고 1N-HCl을 가하여 pH = 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (50 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM) 로 정제하여 고체상태의 목적화합물 31 mg (52% 수율)을 얻었다.3-oxo-cyclohexyl-1-Line-1-yl 3 - (((2 H -1,2,3- triazol-2-yl) methoxy) methoxy) -2-methyl-4- (methylsulfonyl (0.028 mL, 0.21 mmol), potassium cyanide (9.0 mg, 0.138 mmol) and acetone cyanohydrin were added in a catalytic amount (1 drop) Followed by stirring at room temperature for 8 hours. After confirming the completion of the reaction by TLC, the reaction solution was diluted with water (30 mL), acidified to pH = 3 with 1N HCl, extracted with ethyl acetate (50 mL), washed with water and brine I did it. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 31 mg (52% yield) of the desired compound as a solid.

1H NMR (300 MHz, CDCl3) δ 7.88 (d, 1H, J = 8.3 Hz), 7.73 (s, 2H), 7.02 (d, 1H, J = 8.3 Hz), 6.04 (s, 2H), 5.38 (s, 2H), 3.28 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.25 (s, 3H), 2.09 (m, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.88 (d, 1H, J = 8.3 Hz), 7.73 (s, 2H), 7.02 (d, 1H, J = 8.3 Hz), 6.04 (s, 2H), 5.38 2H), 2.25 (s, 3H), 2.09 (m, 2H), 3.28 (s,

실시예 13. 3-(2-클로로-3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시)-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 51)의 합성Example 13. Synthesis of 3- (2-chloro-3- (2-fluoro-2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -4- (methylsulfonyl) ) -4-hydroxybicyclo [3.2.1] oct-3-en-2-one (Compound No. 51)

4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 2-클로로-3-(2-플루오로-2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-4-(메틸설포닐)벤조에이트 (255 mg)를 아세토나이트릴 3 mL에 녹인 후, 아세톤 시아노하이드린 1 방울, 트리에틸아민 (0.15 mL), 시안화칼륨 (52 mg)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/다이클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 223 mg (수율 87%)의 원하는 화합물을 얻을 수 있다.2-chloro-3- (2-fluoro-2- (2- ( 2H -1,2,3-triazol- (Methylsulfonyl) benzoate (255 mg) was dissolved in acetonitrile (3 mL), and then one drop of acetone cyanohydrin, triethylamine (0.15 mL) and potassium cyanide (52 mg The reaction mixture was stirred at room temperature for 12 hours or longer, and the solvent was concentrated under reduced pressure when the reaction was completed. The reaction mixture was acidified by the addition of a 1N aqueous solution of hydrogen chloride and then extracted three times with 10% methanol / dichloromethane . The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography gave 223 mg (87% yield) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.80 (s, 2H), 7.15 (d, J = 8.3 Hz, 1H), 7.01 (dt, J = 50.6, 6.0 Hz, 1H), 5.09-4.92 (m, 2H), 3.19 (s, 3H), 3.04-3.03 (m, 1H), 2.91-2.89 (m, 1H), 1.99-1.91 (m, 4H), 1.79-1.66 (m, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.80 (s, 2H), 7.15 (d, J = 8.3 Hz, 1H), 7.01 (dt, J = 50.6, 2H), 3.19 (s, 3H), 3.04-3.03 (m, 1H), 2.91-2.89 -1.66 (m, 2H)

실시예 14. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 53)의 합성Example 14. Preparation of 2- (3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) Synthesis of cyclohex-1-en-1-yl acetate (Compound No. 53)

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (55 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸클로라이드 (0.01 mL)와 N,N-다이이소프로필에틸아민 (0.02 mL)을 첨가한 후 상온에서 20분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 28.3 mg(47%)의 원하는 화합물을 얻을 수 있다. 2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (55 mg) was dissolved in tetrahydrofuran, acetyl chloride (0.01 mL) and N, N -diisopropylethylamine (0.02 mL) were added and stirred at room temperature for 20 minutes. After the reaction was completed, the reaction mixture was extracted with water and ethyl acetate. The obtained organic layer can be subjected to column chromatography to remove the solvent, and 28.3 mg (47%) of the desired compound can be obtained.

1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.5 Hz, 1H), 7.68 (s, 2H), 7.45 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz, 2H), 4.70 (t, J = 5.0 Hz, 2H), 3.21 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.15 (s, 3H), 2.14-2.12 (m, 2H)
 1 H NMR (500 MHz, CDCl 3) δ 7.91 (d, J = 8.5 Hz, 1H), 7.68 (s, 2H), 7.45 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz , 2H), 4.70 (t, J = 5.0 Hz, 2H), 3.21 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.15 (s , ≪ / RTI > 3H), 2.14-2.12 (m, 2H)

실시예 15. 3-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 아세테이트 (화합물번호 59)의 합성Example 15. Preparation of 3- (3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) Synthesis of bicyclo [3.2.1] ox-2-yl-2-yl acetate (Compound No. 59)

3-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)4-하이드록시바이사이클로[3.2.1]옥-3-엔-2-온사이클로헥-2-센-1-온 (58 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸클로라이드 (0.01 mL)와 N,N-다이이소프로필에틸아민 (0.02 mL)을 첨가한 후 상온에서 20분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 23.5 mg(37%)의 원하는 화합물을 얻을 수 있다. 3- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) 4-hydroxy-bicyclo [3.2 Yl) cyclohex-2-en-1-one (58 mg) was dissolved in tetrahydrofuran, and then acetyl chloride (0.01 mL) and N, N- diisopropylethylamine (0.02 mL) was added thereto, followed by stirring at room temperature for 20 minutes. After the reaction was completed, the reaction mixture was extracted with water and ethyl acetate. The obtained organic layer can be purified by column chromatography to obtain 23.5 mg (37%) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.34 (d, J = 8.1Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.69 (t, J = 5.2 Hz, 2H), 3.20 (s, 3H), 3.06-3.00 (m, 2H), 2.19 (s, 3H), 2.15-1.73 (m, 6H)
 1 H NMR (500 MHz, CDCl 3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.34 (d, J = 8.1Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.69 (t, J = 5.2 Hz, 2H), 3.20 (s, 3H), 3.06-3.00 (m, 2H), 2.19 (s, 3H), 2.15-1.73 (m, 6H)

실시예 16. 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 61)의 합성Example 16.) -2-chloro-4- (methylsulfonyl) 3- (4- (2- (2- (2 H -1,2,3- triazol-2-yl)) Benzoyl) -4-hydroxybicyclo [3.2.1] oct-3-en-2-one (Compound No. 61)

4-옥소바이사이클로[3.2.1]옥트-2-엔-2-일 3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트(3.53 mmol)를 아세토나이트릴 9 mL에 녹인 후, 트리에틸아민 (7.06 mmol), 시안화칼륨 (5.29 mmol), 아세톤 시아노하이드린 3방울을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반 시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산처리한 다음, 에틸아세테이트로 추출하였다. 유기층은 무수황산마그네슘을 이용하여 건조하고 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 0.90g(50%)의 원하는 화합물을 얻을 수 있다.4-oxo-bicyclo [3.2.1] oct-2-en-2-one 3- (a 2- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) (3.53 mmol) was dissolved in acetonitrile (9 mL), triethylamine (7.06 mmol), potassium cyanide (5.29 mmol) and 3 drops of acetone cyanohydrin . The reaction mixture was stirred at room temperature for 12 hours or longer, and when the reaction was completed, the solvent was concentrated under reduced pressure. A 1N aqueous solution of hydrogen chloride was added and acid treatment was performed, followed by extraction with ethyl acetate. The organic layer is dried over anhydrous magnesium sulfate and the solvent is removed, and 0.90 g (50%) of the desired compound can be obtained by column chromatography.

1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.1Hz, 1H), 7.63 (s, 2H), 7.11 (d, J = 8.0Hz, 1H), 4.69 (t, J = 5.6Hz, 2H), 4.37 (t, J = 4.4Hz, 2H), 4.14-1.12 (m, 2H), 3.89 (t, J = 4.5Hz, 2H), 3.28 (s, 3H), 3.19 (t, J = 5.4Hz, 1H), 2.92 (t, J = 6.4Hz, 1H), 2.26-1.76 (m, 6H)
 1 H NMR (500 MHz, CDCl 3) δ 7.95 (d, J = 8.1Hz, 1H), 7.63 (s, 2H), 7.11 (d, J = 8.0Hz, 1H), 4.69 (t, J = 5.6Hz , 2H), 4.37 (t, J = 4.4Hz, 2H), 4.14-1.12 (m, 2H), 3.89 (t, J = 4.5Hz, 2H), 3.28 (s, 3H), 3.19 (t, J = 5.4 Hz, 1 H), 2.92 (t, J = 6.4 Hz, 1 H), 2.26-1.76 (m, 6H)

실시예 17. 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 사이클로프로판카르복실레이트 (화합물번호 63)의 합성Example 17.) -2-chloro-4- (methylsulfonyl) 3- (3- (2- (2- (2 H -1,2,3- triazol-2-yl)) Benzoyl) -4-oxobicyclo [3.2.1] oct-2-yl-cyclopropanecarboxylate (Compound No. 63)

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (64 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸클로라이드 (0.01 mL)와 N,N-다이이소프로필에틸아민 (0.02 mL)을 첨가한 후 상온에서 20분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 36.6 mg (53%)의 원하는 화합물을 얻을 수 있다. () -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 (64 mg) was dissolved in tetrahydrofuran, and then acetyl chloride (0.01 mL) and N, N -diisopropylethylamine (0.02 mL ) Was added thereto, and the mixture was stirred at room temperature for 20 minutes. After the reaction was completed, the reaction mixture was extracted with water and ethyl acetate. The obtained organic layer can be purified by column chromatography to obtain 36.6 mg (53%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.61 (s, 2H), 7.30 (d, J = 8.2Hz, 1H), 4.67 (t, J = 5.6 Hz, 2H), 4.33 (t, J = 4.1 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 3.86 (t, J = 4.3 Hz, 2H), 3.24 (s, 3H), 3.05-3.04 (m, 2H), 2.16-2.07 (m, 4H), 1.75-1.59 (m, 3H), 1.04-1.01 (m, 4H)
 1 H NMR (300 MHz, CDCl 3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.61 (s, 2H), 7.30 (d, J = 8.2Hz, 1H), 4.67 (t, J = 5.6 Hz , 2H), 4.33 (t, J = 4.1 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 3.86 (t, J = 4.3 Hz, 2H), 3.24 (s, 3H), 3.05-3.04 (m, 2H), 2.16-2.07 (m, 4H), 1.75-1.59 (m, 3H), 1.04-1.01

실시예 18. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 67)의 합성Example 18. 2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) Synthesis of 3-oxocyclohex-1-en-1-yl acetate (Compound No. 67)

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (0.21 mmol)을 테트라하이드로퓨란 3 mL에 녹인 후, 다이이소프로필에틸아민 (0.23 mmol)를 첨가하였다. 0℃에서 아세틸클로라이드 (0.23 mmol)를 넣은 후 상온에서 20분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 39.6 mg(36%)의 원하는 화합물을 얻을 수 있다. () -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 2-3 -Hydroxycyclohex-2-en-1-one (0.21 mmol) was dissolved in 3 mL of tetrahydrofuran, and diisopropylethylamine (0.23 mmol) was added. Acetyl chloride (0.23 mmol) was added at 0 占 폚, and the mixture was stirred at room temperature for 20 minutes. After the reaction was completed, the reaction mixture was extracted with water and ethyl acetate. The obtained organic layer can be purified by column chromatography to obtain 39.6 mg (36%) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.44 (d, J = 8.2Hz, 1H), 4.69 (t, J = 5.7 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.6 Hz, 2H), 3.26 (s, 3H), 2.77 (t, J = 6.2 Hz, 2H), 2.54 (t, J = 6.5 Hz, 2H), 2.17 (s, 3H), 2.15-2.14 (m, 2H)
 1 H NMR (500 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.44 (d, J = 8.2Hz, 1H), 4.69 (t, J = 5.7 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.6 Hz, 2H), 3.26 (s, 3H), 2.77 (t , J = 6.2 Hz, 2H) , 2.54 (t, J = 6.5 Hz, 2H), 2.17 (s, 3H), 2.15-2.14 (m, 2H)

실시예 19. (E)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 72)의 합성Example 19 Synthesis of ( E ) -2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) -4- (methylsulfonyl) benzoyl) -3-oxocyclohex-1-en-1-yl acetate (Compound No. 72)

(E)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (100 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸 클로라이드 (0.02 mL), N,N-다이이소프로필에틸아민 (0.04 mL)을 첨가하였다. 반응 혼합물을 상온에서 5분간 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시킨 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 80 mg의 원하는 화합물을 얻을 수 있다. ( E ) -2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) (100 mg) was dissolved in tetrahydrofuran, and then acetyl chloride (0.02 mL), N, N -diisopropylethylamine ( 0.04 mL). The reaction mixture was stirred at room temperature for 5 minutes, and when the reaction was completed, the solvent was concentrated under reduced pressure and then extracted three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. 80 mg of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.44 (d, J = 8.1 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.4 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.76 (t, J = 5.8 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 3H), 2.14 (s, 3H)
 1 H NMR (300 MHz, CDCl 3) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.44 (d, J = 8.1 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.12 (m, 1H ), 5.14 (d, J = 5.4 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.76 (t, J = 5.8 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 3H), 2.14 (s,

실시예 20. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 77)의 합성Example 20 2- (3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-methyl- 4- nitrobenzoyl) -3-oxocyclohexy- Synthesis of 1-sen-1-yl acetate (Compound No. 77)

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(나이트로벤조일)벤조일)-3-하이드록시사이클로헥-2-센-1-온 60 mg (0.155 mmol)을 5 mL의 테트라하이드로퓨란에 녹이고 얼음 중탕을 이용하여 냉각시킨 다음, N,N-다이이소프로필에틸아민 0.08 mL (0.43 mmol)을 첨가하고 계속해서 아세틸 클로라이드 (0.02 mL, 0.28 mmol)을 가한 후 1시간 동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 에틸 아세테이트 (50 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 1/1.5) 로 정제하여 거품상태의 목적화합물 60 mg (90% 수율)을 얻었다. 2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (nitro-benzoyl) benzoyl) -3-hydroxy-cyclohexyl- 2-ene-1-one 60 mg (0.155 mmol) was dissolved in 5 mL of tetrahydrofuran, cooled with ice bath, and 0.08 mL (0.43 mmol) of N, N -diisopropylethylamine Acetyl chloride (0.02 mL, 0.28 mmol) was added thereto, followed by stirring for 1 hour. After confirming the completion of the reaction by TLC, the reaction solution was diluted with water and washed with water and brine while extracting with ethyl acetate (50 mL). The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 1 / 1.5) to obtain 60 mg (90% yield) of the desired compound in the form of a foam.

1H NMR (300 MHz, CDCl3) δ 7.69 (s, 2H), 7.62 (d, 1H, J = 8.5 Hz), 7.31 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.53 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.17 (s, 3H), 2.15 (m, 2H), 2.08 (s, 3H)
1 H NMR (300 MHz, CDCl 3) δ 7.69 (s, 2H), 7.62 (d, 1H, J = 8.5 Hz), 7.31 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.53 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.17 (s, 3H)

실시예 21. (Z)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 78)의 합성Example 21 Synthesis of (Z) -2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) -4- (methylsulfonyl) benzoyl) -3-oxocyclohex-1-en-1-yl acetate (Compound No. 78)

(Z)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (72 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸 클로라이드 (0.01 mL), N,N-다이이소프로필에틸아민 (0.03 mL)을 첨가하였다. 반응 혼합물을 상온에서 5분간 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시킨 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 33 mg의 원하는 화합물을 얻을 수 있다.( Z ) -2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) (72 mg) was dissolved in tetrahydrofuran, and then acetyl chloride (0.01 mL) and N, N -diisopropylethylamine ( 0.03 mL). The reaction mixture was stirred at room temperature for 5 minutes, and when the reaction was completed, the solvent was concentrated under reduced pressure and then extracted three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. 33 mg of the desired compound can be obtained by column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.13-6.25 (m, 1H), 6.01-6.13 (m, 1H), 5.30 (d, J = 6.2 Hz, 2H), 4.95 (d, J = 6.7 Hz, 2H), 3.29 (s, 3H), 2.79 (t, J = 6.0 Hz, 2H), 2.55 (t, J = 6.2 Hz, 2H), 2.09-2.23 (m, 5H)
 1 H NMR (300 MHz, CDCl 3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.13-6.25 (m, 1H), 6.01-6.13 (m, 1H ), 5.30 (d, J = 6.2 Hz, 2H), 4.95 (d, J = 6.7 Hz, 2H), 3.29 (s, 3H), 2.79 (t, J = 6.0 Hz, 2H), 2.55 (t, J = 6.2 Hz, 2H), 2.09-2.23 (m, 5H)

실시예 22. 3-(2-클로로-3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시)-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 아세테이트 (화합물번호 83)의 합성Example 22 3- (2-Chloro-3- (2-fluoro-2- (2 H -1,2,3-triazol-2-yl) ethoxy) -4- (methylsulfonyl) ) -4-oxobicyclo [3.2.1] oct-2-yl-2-yl acetate (Compound No. 83)

3-(2-클로로-3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시)-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (73 mg)을 테트라하이드로퓨란 1 mL에 녹인 후, 다이이소프로필에틸아민 (0.028 mL)를 첨가하였다. 0℃에서 아세틸클로라이드 (0.012 mL)를 넣은 후 상온에서 10분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 41.8 mg (53%)의 원하는 화합물을 얻을 수 있다. 3- (2-Chloro-3- (2-fluoro-ethoxy-2- (2 H -1,2,3- triazol-2-yl)) 4- (methylsulfonyl) benzoyl) -4 Hydroxybicyclo [3.2.1] oct-3-en-2-one (73 mg) was dissolved in 1 mL of tetrahydrofuran, and diisopropylethylamine (0.028 mL) was added. Acetyl chloride (0.012 mL) was added at 0 ° C, and the mixture was stirred at room temperature for 10 minutes. After the reaction was completed, the reaction mixture was extracted with water and ethyl acetate. The obtained organic layer can be purified by column chromatography to obtain 41.8 mg (53%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.40 (d, J = 8.2 Hz, 1H), 7.01 (dt, J = 50.9, 5.8 Hz, 1H), 5.07-4.95 (m, 2H), 3.20 (s, 3H), 3.10-3.01 (m, 2H), 2.23 (s, 3H), 2.21-2.13 (m, 4H), 1.84-1.72 (m, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.40 (d, J = 8.2 Hz, 1H), 7.01 (dt, J = 50.9, 3H), 2.23 (s, 3H), 2.21-2.13 (m, 4H), 1.84-1.72 (m, 2H) (m, 2H)

실시예 23. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 85)의 합성 Example 23 () -2-chloro-4- (methylsulfonyl) to 3- (2- (2 H -1,2,3- triazol-2-yl) benzoyl) -3-chloro-2- Cyclohex-2-en-1-one (Compound No. 85)

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온을 다이클로로메탄에 녹인 후 온도를 0℃로 낮추었다. 0℃ 온도를 유지시키면서 옥살릴클로라이드, N,N-다이메틸포름아마이드 1 방울을 첨가하였다. 반응 혼합물을 상온에서 3시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 반응 혼합물을 물과 에틸아세테이트로 추출한 다음, 얻어진 유기층을 무수황산나트륨을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 원하는 화합물 100 mg (56%)의 원하는 화합물을 얻을 수 있다. 2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one was dissolved in dichloromethane and the temperature was lowered to 0 ° C. One drop of oxalyl chloride, N, N -dimethylformamide , was added while maintaining the temperature at 0 < 0 > C. The reaction mixture was stirred at room temperature for 3 hours or more, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was extracted with water and ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate and the solvent was removed. Column chromatography affords the desired compound in the amount of 100 mg (56%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.86 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.3 Hz, 2H), 2.15 (quin, J = 6.8 Hz, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.86 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.3 Hz, 2H), 2.15 (quin , ≪ / RTI > J = 6.8 Hz, 2H)

실시예 24. 2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 86)의 합성Example 24. 2- (3- (4- (2 H -1,2,3- triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-chloro Cyclohex-2-en-1-one (Compound No. 86)

2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (100 mg)을 다이클로로메탄에 녹인 후 온도를 0℃로 낮추었다. 온도를 유지시키면서 옥살릴클로라이드, N,N-다이메틸포름아마이드 1 방울을 첨가하였다. 반응 혼합물을 상온에서 3시간 이상 교반 시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 반응 혼합물을 물과 에틸아세테이트로 추출한 다음, 얻어진 유기층을 무수황산나트륨을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 원하는 화합물 18 mg(18%)의 원하는 화합물을 얻을 수 있다. 2- (3- (4- (2 H -1,2,3- triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (100 mg) was dissolved in dichloromethane and the temperature was lowered to 0 ° C. One drop of oxalyl chloride, N, N -dimethylformamide , was added while maintaining the temperature. The reaction mixture was stirred at room temperature for 3 hours or more, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was extracted with water and ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate and the solvent was removed. Column chromatography afforded the desired compound in 18 mg (18%) of desired compound.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.3 Hz, 1H), 7.61 (s, 2H), 7.56 (d, J = 8.3 Hz, 1H), 4.58 (t, J = 7.0 Hz, 2H), 4.26 (t, J = 6.2 Hz, 2H), 3.24 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.26-2.16 (m, 4H), 1.93-1.88 (m, 2H)
 1 H NMR (300 MHz, CDCl 3) δ 7.93 (d, J = 8.3 Hz, 1H), 7.61 (s, 2H), 7.56 (d, J = 8.3 Hz, 1H), 4.58 (t, J = 7.0 Hz , 2H), 4.26 (t, J = 6.2 Hz, 2H), 3.24 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.26-2.16 (m, 4 H), 1.93 - 1.88 (m, 2 H)

실시예 25. 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 94)의 합성Example 25.) -2-chloro-4- (methylsulfonyl) 3- (3- (2- (2- (2 H -1,2,3- triazol-2-yl)) Benzoyl) -4-chlorobicyclo [3.2.1] oct-3-en-2-one (Compound No. 94)

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)바이사이클로[3.2.1]옥탄-2,4-다이온 (0.2 mmol)을 다이클로로메탄에 녹인 후 온도를 0℃로 낮추었다. 온도를 유지시키면서 옥살릴 클로라이드 (0.3 mmol), N,N-다이메틸포름아마이드 1 방울을 첨가하였다. 반응 혼합물을 상온에서 3시간 이상 교반 시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 반응 혼합물을 물과 에틸아세테이트로 추출한 다음, 얻어진 유기층을 무수황산나트륨을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 원하는 화합물 34.1 mg(32%)의 원하는 화합물을 얻을 수 있다.3- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) bicyclo [3.2.1] octane-2,4-dione (0.2 mmol) was dissolved in dichloromethane and the temperature was lowered to 0 ° C. Oxalyl chloride (0.3 mmol) and 1 drop of N, N -dimethylformamide were added while maintaining the temperature. The reaction mixture was stirred at room temperature for 3 hours or more, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was extracted with water and ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate and the solvent was removed. Column chromatography afforded 34.1 mg (32%) of the desired compound as the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.35 (t, J = 4.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.27 (S, 3H), 3.24 (t, J = 4.8 Hz, 1H), 3.07 (t, J = 6.5 Hz, 1H), 2.34-1.95 (m, 6H)
 1 H NMR (500 MHz, CDCl 3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.35 (t, J = 4.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.27 (S, 3H), 3.24 (t J = 4.8 Hz, 1H), 3.07 (t, J = 6.5 Hz, 1H), 2.34-1.95 (m, 6H)

실시예 26. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 95)의 합성 Example 26. Preparation of 2- (3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) Cyclohex-2-en-1-one (Compound No. 95)

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 60 mg (0.143 mmol)을 5 mL의 다이클로로메탄에 녹이고 옥살일 클로라이드 (0.06 mL, 0.71 mmol)을 첨가하고 다이메틸포름아마이드 1 방울을 가한 후 상온에서 2시간 동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 에틸 아세테이트 (50 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 1/1)로 정제하여 거품상태의 목적화합물 55 mg (88% 수율)을 얻었다. 2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-one -one 60 mg (0.143 mmol) was dissolved in 5 mL of dichloromethane. Oxalyl chloride (0.06 mL, 0.71 mmol) was added, and 1 drop of dimethylformamide was added thereto, followed by stirring at room temperature for 2 hours Respectively. After confirming the completion of the reaction by TLC, the reaction solution was diluted with water and washed with water and brine while extracting with ethyl acetate (50 mL). The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 1/1) to obtain 55 mg (88% yield) of the desired compound in the form of a foam.

1H NMR (300 MHz, CDCl3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.71 (s, 2H), 7.39 (d, 1H, J = 8.3 Hz), 4.95 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.90 (t, 2H), 2.54 (t, 2H), 2.30 (s, 3H), 2.22 (m, 2H)
1 H NMR (300 MHz, CDCl 3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.71 (s, 2H), 7.39 (d, 1H, J = 8.3 Hz), 4.95 (t, 2H), 4.56 2H), 3.25 (s, 3H), 2.90 (t, 2H), 2.54

실시예 27. 2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-플루오로사이클로헥-2-센-1-온 (화합물번호 118)의 합성Example 27. Preparation of 2- (3- (3- (2 H -1,2,3-triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) 2-en-1-one (Compound No. 118)

2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥스-2-에논 (0.13 mmol)을 다이클로로메탄 3 mL에 녹인 후, 0℃에서 다이에틸아미노설퍼 트라이플로라이드 (0.39 mmol)를 첨가하였다. 상온에서 18시간 이상 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 13.1 mg (22%)의 원하는 화합물을 얻을 수 있다. 2- (3- (3- (2 H -1,2,3- triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclo hex- 2-enone (0.13 mmol) was dissolved in 3 mL of dichloromethane, and then diethylaminosulfur trifluoride (0.39 mmol) was added at 0 ° C. The mixture was stirred at room temperature for 18 hours or longer. After the reaction was completed, the reaction mixture was extracted with water and ethyl acetate. The obtained organic layer was subjected to column chromatography to remove the solvent, and 13.1 mg (22%) of the desired compound could be obtained.

1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.30 (d, J = 8.1 Hz, 1H), 4.74 (t, J = 7.1 Hz, 2H), 4.31 (t, J = 6.0 Hz, 2H), 3.26 (s, 3H), 2.61-1.95 (m, 8H)
1 H NMR (300 MHz, CDCl 3) δ 7.94 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.30 (d, J = 8.1 Hz, 1H), 4.74 (t, J = 7.1 Hz , 2H), 4.31 (t, J = 6.0 Hz, 2H), 3.26 (s, 3H), 2.61-1.95 (m, 8H)

실시예 28. 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 120)의 합성Example 28. 2- (3- (2- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) benzoyl-2-methyl-4-nitro) - Synthesis of 3-hydroxycyclohexyl-2-sen-1-one (Compound No. 120)

3-옥소사이클로헥-1-센-1-일 3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조에이트 125 mg (0.29 mmol)을 아세토니트릴 7 mL에 녹이고 트리에틸아민 (0.06 mL), 시안화칼륨 (19 mg) 그리고 아세톤 시아노하이드린을 촉매량 (1 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 1N-HCl을 가하여 pH = 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM)로 정제하여 목적화합물 100 mg (68% 수율)을 얻었다.3-oxocyclohex-1-en-1-yl 3- (2- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) ethoxy) 125 mg (0.29 mmol) of sodium nitrite was dissolved in 7 mL of acetonitrile, and a catalytic amount (1 drop) of triethylamine (0.06 mL), potassium cyanide (19 mg) and acetone cyanohydrin was added thereto at room temperature for 8 hours Lt; / RTI > After confirming the completion of the reaction by TLC, the reaction solution was diluted with water, 1 N HCl was added to make an acidic solution of pH = 3, and the mixture was extracted with ethyl acetate (100 mL) and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain the desired compound (100 mg, 68% yield).

1H NMR (300 MHz, CDCl3) δ 7.70 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 6.92 (d, 1H, J = 8.4 Hz), 4.66 (t, 2H), 4.13 (t, 2H), 4.08 (t, 2H), 3.79 (t, 2H), 2.84 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H)
1 H NMR (300 MHz, CDCl 3) δ 7.70 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 6.92 (d, 1H, J = 8.4 Hz), 4.66 (t, 2H), 4.13 2H), 4.08 (t, 2H), 3.79 (t, 2H), 2.84 (t, 2H), 2.46

실시예 29. 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 123)의 합성 Example 29. 2- (3- (2- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) Benzoyl) -3-hydroxycyclohexyl-2-en-1-one (Compound No. 123)

3-옥소사이클로헥-1-센-1-일 3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조에이트 165 mg (0.356 mmol)을 아세토니트릴 10 mL에 녹이고 트리에틸아민 (0.09 mL), 시안화칼륨 (28 mg) 그리고 아세톤 시아노하이드린을 촉매량 (1 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 1N-HCl을 가하여 pH = 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM) 로 정제하여 목적화합물 100 mg (60% 수율)을 얻었다.3-oxocyclohex-1-en-1-yl 3- (2- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) ethoxy) (Methylsulfonyl) benzoate (165 mg, 0.356 mmol) was dissolved in acetonitrile (10 mL), and a catalytic amount (1 drop) of triethylamine (0.09 mL), potassium cyanide (28 mg) and acetone cyanohydrin Lt; / RTI > for 8 hours. After confirming the completion of the reaction by TLC, the reaction solution was diluted with water, 1 N HCl was added to make an acidic solution of pH = 3, and the mixture was extracted with ethyl acetate (100 mL) and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain the desired compound (100 mg, 60% yield).

1H NMR (300 MHz, CDCl3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.98 (d, 1H, J = 8.4 Hz), 4.69 (t, 2H), 4.20 (t, 2H), 4.12 (t, 2H), 3.84 (t, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H)
1 H NMR (300 MHz, CDCl 3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.98 (d, 1H, J = 8.4 Hz), 4.69 (t, 2H), 4.20 2H), 3.18 (t, 2H), 3.84 (t, 2H), 3.26 (s, 3H), 2.83 m, 2H)

통상의 당업자라면 상기 실시예에서 예시된 합성법을 이용하거나 응용하여 상기 표 1에 예시한 화합물들을 쉽게 합성할 수 있다.
Those skilled in the art will readily be able to synthesize the compounds illustrated in Table 1 using or employing the synthetic methods illustrated in the above Examples.

[제제][Agent]

본 발명의 상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물은 제초제로서 유용하게 사용할 수 있으며, 제초제로 사용하는 경우 농약의 제제화에 통상적으로 사용하는 담체, 계면활성제, 분산제, 보조제 등을 상기 화학식 1의 화합물과 배합하여 수화제, 유제, 분제 현탁제, 액제 등의 각종 형태로 제제화하여 사용할 수 있다. 이들 제제들은 직접 사용될 수 있고 적절한 매체에 희석하여 처리할 수 있다. The benzoylcyclohexanedione compound represented by Formula 1 of the present invention can be used as a herbicide. When a herbicide is used, a carrier, a surfactant, a dispersant, an adjuvant, Can be formulated into various forms such as a wetting agent, an emulsion, a suspension suspending agent, a liquid agent, and the like. These preparations can be used directly and can be diluted in suitable media for treatment.

분무 부피량은 헥타아르(ha)당 수 백 리터 내지 몇 천 리터까지 사용할 수 있다.The spray volume can be from several hundred liters to several thousand liters per hectare (ha).

본 발명의 제초제 조성물은 상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 1종 이상의 활성성분 0.1 중량% 내지 99.9 중량%; 및 계면활성제, 및 고체 또는 액체 희석제로부터 선택된 1종 또는 2종 이상의 첨가제 0.1 중량% 내지 99.9 중량%; 를 포함한다.The herbicidal composition of the present invention comprises 0.1% by weight to 99.9% by weight of at least one active ingredient selected from the group consisting of benzoylcyclohexane dione compounds represented by the formula (1) and pesticidally acceptable salts thereof; And 0.1% to 99.9% by weight of one or more additives selected from a surfactant, and a solid or liquid diluent; .

상기 제초제 조성물은 활성성분을 0.1 중량% 내지 99.9 중량% 범위로 포함할 수 있고, 제제 형태에 따라 활성성분의 함량을 차이가 있을 수 있다. 또한, 상기 제초제 조성물에는 0.1 중량% 내지 99.9 중량% 범위로 포함할 수 있다. 상기 첨가제는 계면활성제, 고체 희석제 또는 액체 희석제일 수 있으며, 계면활성제는 약 0.1 중량% 내지 20 중량% 범위로 함유될 수 있고, 고체 또는 액체 희석제는 0 중량% 내지 99. 9중량% 범위로 함유시킬 수도 있다. The herbicidal composition may contain the active ingredient in an amount ranging from 0.1% by weight to 99.9% by weight, and the content of the active ingredient may vary depending on the form of the preparation. Also, the herbicide composition may contain 0.1% by weight to 99.9% by weight. The additive may be a surfactant, a solid diluent or a liquid diluent, the surfactant may be present in the range of about 0.1% to 20% by weight, the solid or liquid diluent in the range of 0% to 99.9% .

하기 표 3에는 제제의 형태별로 활성성분, 계면활성제 및 희석제의 함량을 대략적으로 요약하여 나타내었다.In Table 3, the contents of the active ingredient, surfactant and diluent are roughly summarized for each type of preparation.

제형Formulation 함량비 (단위: 중량%)Content ratio (unit:% by weight) 활성성분Active ingredient 계면활성제Surfactants 희석제diluent 수화제Hydrating agent 10 ∼ 9010 to 90 1 ∼ 101 to 10 0 ∼ 800 to 80 현탁제Suspension 3 ∼ 503 to 50 0 ∼ 150 to 15 40 ∼ 9540 to 95 유제/액제Emulsion / liquid 3 ∼ 503 to 50 0 ∼ 150 to 15 40 ∼ 9540 to 95 입제Granulation 0.1 ∼ 950.1 to 95 1 ∼ 151 to 15 5 ∼ 99.55 to 99.5

상기 계면활성제는 계면활성이 큰 물질이며, 분자 중에 친수성 및 친유성 분자단을 가진 양친매성 물질일 수 있다. 이러한 계면활성제는 세정력, 분산력, 유화력, 가용화력, 습윤력, 살균력, 기포력 및 침투력 등이 우수하므로, 제조체 조성물에 포함되어 효과적으로 약효를 발현하도록 습윤, 붕괴, 분산, 또는 유화시키는 작용을 한다. 상기 계면활성제로는 (C8∼C12알킬)벤젠설포네이트, (C3∼C6알킬)나프탈렌설포네이트, 다이(C3∼C6알킬)나프탈렌설포네이트, 다이(C8∼C12알킬)설포석시네이트, 리그닌설포네이트, 나프탈렌설포석시네이트포르말린축합물, (C8∼C12알킬)나프탈렌설포네이트포르말린축합물, 폴리옥시에틸렌(C8∼C12알킬)페닐설포네이트와 같은 설포네이트의 나트륨염 또는 칼슘염; (C8∼C12알킬)설페이트, 폴리옥시에틸렌(C8∼C12알킬)설페이트, 폴리옥시에틸렌(C8∼C12알킬)페닐설페이트와 같은 설페이트의 나트륨염 또는 칼슘염; 폴리옥시알킬렌숙시네이트와 같은 숙시네이트의 나트륨염 또는 칼슘염; 등이 포함되는 음이온성 계면활성제알 수 있다. 또한 상기 계면활성제로는 폴리옥시에틸렌(C8∼C12알킬)에테르, 폴리옥시에틸렌(C8∼C12알킬)페닐에테르, 폴리옥시에틸렌(C8∼C12알킬)페닐폴리머와 같은 비이온성 계면활성제가 포함될 수 있다. 상기한 계면활성제는 단독 또는 2종 이상을 혼합되어 사용될 수 있으며, 본 발명에서 사용될 수 있는 계면활성제가 상기 예시적으로 열거된 화합물에 한정되지 아니한다.The surfactant may be an amphipathic substance having a large surface activity and having hydrophilic and lipophilic molecular chains in the molecule. Such surfactants are excellent in washing power, dispersing power, emulsifying power, solubilizing power, wetting power, sterilizing power, bubble power and penetration power, and thus have a function of wetting, disintegrating, dispersing, or emulsifying . Examples of the surfactant include (C 8 -C 12 alkyl) benzenesulfonate, (C 3 -C 6 alkyl) naphthalenesulfonate, di (C 3 -C 6 alkyl) naphthalenesulfonate, dies (C 8 -C 12 alkyl ) sulfosuccinate, lignin sulfonate, naphthalene sulfosuccinate formalin condensate, (C 8 ~C 12 alkyl) naphthalene sulfonate-formaldehyde condensate, polyoxyethylene (C 8 ~C 12 alkyl), such as a phenyl sulfonate Sodium or calcium salts of sulfonates; (C 8 ~C 12 alkyl) sulfates, polyoxyethylene (C 8 ~C 12 alkyl) sulfates, polyoxyethylene (C 8 ~C 12 alkyl) sulfate, sodium or calcium salts of sulfate such as phenyl; Sodium salt or calcium salt of succinate such as polyoxyalkylene succinate; And the like may be known as the anionic surfactant. Examples of the surfactant include nonionic surfactants such as polyoxyethylene (C 8 to C 12 alkyl) ether, polyoxyethylene (C 8 to C 12 alkyl) phenyl ether, and polyoxyethylene (C 8 to C 12 alkyl) Surfactants may be included. The above-mentioned surfactants may be used alone or in combination of two or more, and the surfactants that can be used in the present invention are not limited to the above exemplified compounds.

상기 활성성분의 함량은 용도에 따라 조절될 수 있으며, 활성성분에 비하여 계면활성제를 더 많은 함량으로 사용하는 것이 필요할 때도 있으며 제제 시에 첨가하거나 탱크 혼합으로 사용할 수도 있다.The content of the active ingredient may be adjusted depending on the application, and it may be necessary to use a surfactant in an amount higher than that of the active ingredient, and it may be added at the time of formulation or may be used as a tank mix.

본 발명의 제초제 조성물에 포함되는 희석제는 성상에 따라 고체 희석제와 액체 희석제로 분류할 수 있다. 고체 희석제로서 흡수력이 높은 희석제는 수화제를 만들 때 특히 좋다. 액체 희석제와 용제는 0℃에서도 상분리가 일어나지 않고 안정한 것이 좋다. 액체 희석제로는, 물, 톨루엔, 자일렌, 석유 에테르, 식물성 오일, 아세톤, 메틸 에틸 케톤, 사이클로헥사논, 산 무수물, 아세토나이트릴, 아세토페논, 아밀 아세테이트, 2-부타논, 부틸린 카보네이트, 클로로벤젠, 사이클로헥산, 사이클로헥산올, 아세트산의 알킬 에스테르, 다이아세톤 알콜, 1,2-다이클로로프로판, 다이에탄올아민, p-다이에틸벤젠, 다이에틸렌 글리콜, 다이에틸렌 글리콜 아비에테이트, 다이에틸렌 글리콜 부틸 에테르, 다이에틸렌 글리콜 에틸 에테르, 다이에틸렌 글리콜 메틸 에테르, N,N-다이메틸포름아마이드, 다이메틸 설폭사이드, 1,4-다이옥산, 다이프로필렌 글리콜, 다이프로필렌 글리콜 메틸 에테르, 다이프로필렌 글리콜 다이벤조에이트, 디프록시톨, 알킬피롤리돈, 에틸 아세테이트, 2-에틸 헥산올, 에틸렌 카보네이트, 1,1,1-트리클로로에탄, 2-헵타논, 알파-피넨, d-리모넨, 에틸 락테이트, 에틸렌 글리콜, 에틸렌 글리콜 부틸 에테르, 에틸렌 글리콜 메틸 에테르, 감마-부티로락톤, 글리세롤, 글리세롤 아세테이트, 글리세롤 다이아세테이트, 글리세롤 트리아세테이트, 헥사데칸, 헥실렌 글리콜, 이소아밀 아세테이트, 이소보르닐 아세테이트, 이소옥탄, 이소포론, 이소프로필벤젠, 이소프로필 미리스테이트, 락트산, 라우릴아민, 메시틸 옥사이드, 메톡시프로판올, 메틸 이소아밀 케톤, 메틸 이소부틸 케톤, 메틸 라우레이트, 메틸 옥타노에이트, 메틸 올레에이트, 메틸렌 클로라이드, m-자일렌, n-헥산, n-옥틸아민, 옥타데칸산, 옥틸아민 아세테이트, 올레산, 올레일아민, o-자일렌, 페놀, 폴리에틸렌 글리콜(PEG 400), 프로피온산, 프로필 락테이트, 프로필렌 카보네이트, 프로필렌 글리콜, 프로필렌 글리콜 메틸 에테르, p-자일렌, 톨루엔, 트리에틸 포스페이트, 트리에틸렌 글리콜, 자일렌설폰산, 파라핀, 광유, 트리클로로에틸렌, 퍼클로로에틸렌, 에틸 아세테이트, 아밀 아세테이트, 부틸 아세테이트, 프로필렌 글리콜 메틸 에테르, 다이에틸렌 글리콜 메틸 에테르, 메탄올, 에탄올, 이소프로판올, 및 고분자량 알콜, 예를 들어, 아밀 알콜, 테트라하이드로푸르푸릴 알콜, 헥산올, 옥탄올, 에틸렌 글리콜, 프로필렌 글리콜, 글리세롤, N-메틸-2-피롤리돈 등이 사용될 수 있다. 고체 희석제로는 활석, 이산화티탄, 납석 점토, 실리카, 아타펄자이트 점토, 규조토, 석회암, 탄산칼슘, 벤토나이트, 칼슘 몬모릴로나이트, 목화씨 껍질, 통밀가루(wheatmeal), 콩고물, 속돌, 목분, 호두 껍질, 리그닌 등이 사용될 수 있다.The diluent contained in the herbicidal composition of the present invention can be classified into a solid diluent and a liquid diluent depending on the properties. As a solid diluent, a highly absorbing diluent is particularly good when making a wetting agent. The liquid diluent and solvent should be stable at 0 ° C without phase separation. Examples of liquid diluents include water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, But are not limited to, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p -diethylbenzene, diethylene glycol, diethylene glycol abiotate, N, N -dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol diesters such as diethyleneglycol methyl ether, Benzoate, dipropoxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-tri But are not limited to, ethylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, But are not limited to, acetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, M -xylene, n -hexane, n -octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o -xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propyl lactate, propylene carbonate, propylene glycol , Propylene glycol methyl ether, p -xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether , diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohol, e.g., amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N - methyl-2 - pyrrolidone and the like can be used. Solid diluents include talc, titanium dioxide, pyrophyllite, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed peel, wheatmeal, Lignin and the like can be used.

또한, 본 발명의 제초제 조성물을 제제화할 때는 거품생성, 케이크화, 부식발생, 미생물 번식 등을 방지하기 위하여 소량의 기타 첨가제를 가할 수도 있다.When the herbicidal composition of the present invention is formulated, small amounts of other additives may be added to prevent foaming, caking, corrosion, microbial propagation, and the like.

본 발명의 제초제 조성물을 만드는 방법은 통상의 방법에 의해 수행한다. 액제의 경우는 구성성분들을 단지 혼합하기만 하면 되고, 미세 고상 조성물은 햄머 또는 유동 제분기에서 혼합 분쇄하면 된다. 현탁제의 경우는 습식 제분기에 혼화처리하여 만들고 입제는 활성물질을 입제 담체위에 분무하여 제조할 수 있다.The method for producing the herbicidal composition of the present invention is carried out by a conventional method. In the case of a liquid agent, it is sufficient to merely mix the constituents, and the fine solid phase composition may be mixed and pulverized in a hammer or a flow mill. In the case of a suspension, it may be prepared by admixing the wet mill with the active substance sprayed onto the granular carrier.

본 발명에 따른 화합물을 이용한 대표적 제제 제조예는 다음과 같다.
A representative preparation example using the compound according to the present invention is as follows.

제제 1: 수화제Formulation 1: Hydration agent

하기의 성분들을 완전히 혼합하고 액체 계면활성제를 고체성분들 위에 분무하면서 혼합하였다. 햄머 밀에서 분쇄하여 입자크기가 100 ㎛ 이하가 되게 하였다.The following ingredients were mixed thoroughly and mixed with a liquid surfactant sprayed onto the solid ingredients. Followed by pulverization in a hammer mill to make the particle size to be 100 mu m or less.

유효 화합물 20 중량%20% by weight of the active compound

도데실페놀 폴리에틸렌 글리콜 에테르 2 중량%2% by weight of dodecylphenol polyethylene glycol ether

나트륨 리그린 설포네이트 4 중량%4% by weight sodium < RTI ID = 0.0 >

나트륨 실리콘 알루미네이트 6 중량%Sodium silicon aluminate 6 wt%

몬트모릴로나이트 68 중량%
68% by weight of montmorillonite

제제 2: 수화제Formulation 2: Hydration agent

하기의 성분들을 혼합하고 입자크기가 25 ㎛ 이하가 될 때까지 햄머 밀에서 분쇄한 후 포장하였다.The following ingredients were mixed and ground in a hammer mill until the particle size was less than 25 μm and packed.

유효 화합물 80 중량%Effective compound 80 wt%

나트륨 알킬 나프탈렌 설포네이트 2 중량%2% by weight sodium alkylnaphthalene sulfonate

나트륨 리그린 설포네이트 2 중량%2% by weight sodium < RTI ID = 0.0 >

합성 무정형 실리카 3 중량%3% by weight of synthetic amorphous silica

카오리나이트 13 중량%
13% by weight of kaolinite

제제 3: 유제Formulation 3: Emulsion

하기의 성분들을 섞고 균일하게 용해하여 유제로 하였다.The following components were mixed and uniformly dissolved to prepare an emulsion.

유효 화합물 30 중량%30% by weight of the active compound

싸이클로헤사논 20 중량%Cyclohexanone 20 wt%

폴리옥시에틸렌 알킬아릴에테르 11 중량%11 weight% polyoxyethylene alkyl aryl ether < RTI ID = 0.0 >

알킬벤젠설폰산 칼슘 4 중량%4% by weight of calcium alkylbenzenesulfonate,

메틸나프탈렌 35 중량%
Methyl naphthalene 35 wt%

제제 4: 입제Formulation 4: Granulation

하기의 성분들을 균일하게 혼합 분쇄한 후, 이 혼합물 100 중량부에 물 20 중량부를 가하고 혼합하여 압출식 조입기를 사용 14~32 메쉬의 입제로 가공한 후 건조하여 입제를 제조하였다.The following components were uniformly mixed and pulverized, and 20 parts by weight of water was added to 100 parts by weight of the mixture. The mixture was processed into a 14 to 32 mesh granule by using an extrusion type granulator and dried to prepare a granule.

유효 화합물 5 중량%5% by weight active compound

나트륨 라우릴 알콜 황산 에스테르 염 2 중량%Sodium lauryl alcohol sulfate 2%

나트륨 리그린 설포네이트 5 중량%5% by weight sodium < RTI ID = 0.0 >

카르복시메틸 셀룰로오스 2 중량%Carboxymethylcellulose 2 wt%

황산칼륨 16 중량%16% by weight of potassium sulfate,

석고 70 중량%Gypsum 70 wt%

본 발명의 제제는 실제 사용에 있어서는 적당한 농도로 희석하여 살포하였다.
The formulation of the present invention was diluted to an appropriate concentration for practical use.

[용도][Usage]

본 발명에 따른 벤조일사이클로헥산다이온 화합물은 토양에 처리되어 여러 가지 잡초를 방제하는 효과가 탁월하다. 구체적으로, 본 발명에 따른 벤조일사이클로헥산다이온 화합물은 수면처리 또는 경엽처리 되어서는 바람직하지 못한 잡초의 방제효과가 탁월하였다. 본 발명에 따른 벤조일사이클로헥산다이온 화합물은 수면처리 또는 경엽처리 되어서는 벼에 대하여 높은 안전성을 나타내며, 화본과 잡초, 사초과 잡초, 또는 광엽 잡초를 방제하는 효과가 탁월하였다. 특히, 화본과 잡초로서 수수, 돌피, 바랭이; 사초과 잡초로서 올챙이고랭이; 광엽 잡초로서 물달개비, 까마중, 도꼬마리; 에 대한 방제 효능이 우수하다. 따라서 벤조일사이클로헥산다이온 화합물이 활성성분으로 포함된 제초제는 논 농사 및 밭 농사에 적합하다.The benzoylcyclohexanedione compound according to the present invention is excellent in the effect of treating various weeds by treating the soil. Specifically, the benzoylcyclohexanedione compound according to the present invention was excellent in the control of weeds, which are undesirable when subjected to water surface treatment or foliar treatment. The benzoylcyclohexanedione compound according to the present invention exhibits high safety against rice when subjected to a surface treatment or foliage treatment, and has excellent effect of controlling weeds, weeds, weeds, weeds, or weeds. In particular, weeds and weeds such as sorghum, Strawberries as weeds and weeds; Light weed, water falciparum, camphor, doom; Is excellent in control efficacy against. Therefore, herbicides containing benzoylcyclohexanedione compounds as active ingredients are suitable for paddy farming and field farming.

본 발명의 제초제는 유효성분으로 헥타아르(ha)당 10 g 내지 1 kg까지 사용할 수 있는데, 바람직하기로는 10 g 내지 400 g 정도를 사용하는 것이 좋다. 약량의 선택은 잡초 발생량이나 생육정도, 제제 등의 요소에 의해 결정한다. The herbicide of the present invention may be used in an amount of from 10 g to 1 kg per hectare (ha) as an active ingredient, preferably from about 10 g to 400 g. The selection of the dosage is determined by factors such as the amount of weed, the degree of growth, and the formulation.

또, 본 발명의 화합물은 단독으로 사용할 수 있고, 아세틸-CoA 카르복실라제 억제제(ACC), 아세토락테이트 신타제 억제제(ALS), 아마이드, 옥신 제초제, 옥신 수송 억제제, 카로테노이드 생합성 억제제, 에놀피루빌시키메이트 3-포스페이트 신타제 억제제(ESPS), 글루타민 신테타제 억제제, 지질 생합성 억제제, 유사분열 억제제, 프로토포르피리노겐 IX 옥시다제 억제제, 광합성 억제제, 상승작용제, 성장 물질, 세포벽 생합성 억제제 및 기타 제초제로 이루어지는 군으로부터 선택되는 하나 또는 그 이상의 제초 활성 화합물과 혼합하여 사용하는 것도 유용하다. The compounds of the present invention can also be used alone and can be used in combination with acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, (ESPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitotic inhibitors, protoporphyrinogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth materials, cell wall biosynthesis inhibitors and other herbicides It is also useful to mix them with one or more herbicidally active compounds selected from the group consisting of

상기 아세틸-CoA 카르복실라제 억제제(ACC)로는 사이클로헥세논 옥심 에테르로서 알록시딤, 클레토딤, 클로프록시딤, 사이클록시딤, 세톡시딤, 트랄콕시딤, 부트록시딤, 클레폭시딤 또는 테프랄옥시딤, 페녹시페녹시프로피온산 에스테르로서 들어 메타미포프, 시할로포프-부틸, 다이클로포프-메틸, 페녹사프로프-에틸, 페녹사프로프-P-에틸, 펜티아프로프-에틸, 플루아지포프-부틸, 플루아지포프-P-부틸, 할록시포프-에톡시에틸, 할록시포프-메틸, 할록시포프-P-메틸, 이속사피리포프, 프로파퀴즈아포프, 퀴즈알로포프-에틸, 퀴즈알로포프-P-에틸 또는 퀴즈알로포프-테푸릴을 사용할 수 있다. The acetyl-CoA carboxylase inhibitor (ACC) may be selected from cyclohexenone oxime ether such as alloxydim, clethodim, cloproxydim, cycloxydim, cetoxydim, tralcoxydim, butroxydim, clexoxidim Propoxylphenoxypropionate as metaxipop, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, Ethyl, fluazipop-butyl, fluazipop-P-butyl, haloxypop-ethoxyethyl, haloxyp-methyl, haloxyp-P-methyl, isoxaphyropyph, Aloporph-ethyl, quizalofop-P-ethyl or quizalofop-tert-furyl.

상기 아세토락테이트 신타제 억제제(ALS)로는 이미다졸리논로서 이마자피르, 이마자퀸, 이마자메타벤즈-메틸 , 이마자목, 이마자픽, 이마제타피르 또는 이마자메타피르, 피리미딜 에테르로서 피리티오박-산, 피리티오박-나트륨, 비스피리박-나트륨 또는 피리벤즈옥심, 술폰아마이드로서 플로라술람, 플루메트술람 또는 메토술람, 술포닐우레아로서 아미도설퓨론, 아짐설퓨론, 벤설퓨론-메틸, 클로리무론-에틸, 클로르설퓨론, 시노설퓨론, 사이클로설파무론, 에타메트설퓨론-메틸, 에톡시설퓨론, 플라자설퓨론, 할로설퓨론-메틸, 이마조설푸론, 메트설퓨론-메틸, 니코설퓨론, 프리미설퓨론-메틸, 프로설퓨론, 피라조설퓨론-에틸, 림설퓨론, 설퓨메투론-메틸, 티오펜설퓨론-메틸, 트리아설퓨론, 트리베누론-메틸, 트리플루설퓨론-메틸, 술포설퓨론, 플루세토설퓨론 또는 아이오도설퓨론를 사용할 수 있다. Examples of the acetolactate synthetase inhibitor (ALS) include imazapyr, imazapquin, imazamethabenz-methyl, imazamabic, imajapik, imazethapyr or imazamethapyr, pyrimidyl ether as pyrimidyl ether, Thiopalic acid, pyrithiopal-sodium, bispyridyl-sodium or pyridivoxime, sulfonamides such as florasulam, flumethsulam or methosulam, sulfonylurea amidosulfuron, azimulphuron, benzylfuron-methyl , Chlorosulphuron-methyl, imazosulfuron-methyl, methosulfuron-methyl, chlorosulfuron-methyl, chlorosulfuron-methyl, chlorosulfuron, Methylsulfuron-methyl, triisulfuron-methyl, triflusulfuron-methyl, thiosulfuron-methyl, triisulfuron-methyl, Methyl, sulfosulfuron, flucetose Sulfuron or iodosulfuron can be used.

상기 옥신 제초제로는 피리딘 카르복실산으로서 클로피랄리드 또는 피클로람, 2,4-D 또는 베나졸린을 사용할 수 있다.As the auxin herbicide, clopyralide or picloram, 2,4-D or a benzazoline can be used as pyridinecarboxylic acid.

상기 옥신 수송 억제제로는 나프탈람 또는 다이플루펜조피르를 사용할 수 있고 상기 카로테노이드 생합성 억제제로는 벤조페나프, 클로마존, 디플루페니칸, 플루오로클로리돈, 플루리돈, 피라졸리네이트, 피라족시펜, 이속사플루톨, 이속사클로르톨, 메소트리온, 술코트리온 (클로르메술론), 케토스피라독스, 플루르타몬, 노르플루라존 또는 아미트롤을 사용할 수 있다.The auxin transport inhibitor may be naphthalene or diflufenzopyr. Examples of the carotenoid biosynthesis inhibitor include benzophenaf, clomazone, diflufenican, fluorochloridone, pyrrolidone, pyrazolinate, It is possible to use ciliophen, isoxaflutole, isoxaprochlor, methotrione, sulcotrione (chlomethserone), ketospirados, fluulamone, norfluracil or amitrol.

상기 에놀피루빌시키메이트 3-포스페이트 신타제 억제제(ESPS)로는 글리포세이트 또는 술포세이트를 사용할 수 있고, 상기 글루타민 신테타제 억제제로는 빌라나포스(비알라포스) 또는 글루포시네이트-암모늄을 사용할 수 있다.As the above-mentioned enolpyruvylskylmate 3-phosphate synthase inhibitor (ESPS), glyphosate or sulfosate may be used, and as the glutamine synthetase inhibitor, villa napus (bialaphos) or glufosinate-ammonium may be used .

상기 지질 생합성 억제제로는 아닐리드로서 아닐로포스 또는 메페나세트, 클로로아세트아닐리드로서 디메텐아미드, S-디메텐아미드, 아세토클로르, 알라클로르, 부타클로르, 부텐아클로르, 디에타틸-에틸, 디메타클로르, 메타자클로르, 메톨아클로르, S-메톨아클로르, 프레틸아클로르, 프로프아클로르, 프린아클로르, 테르부클로르, 테닐클로르 또는 크실아클로르, 티오우레아로서 부틸레이트, 사이클로에이트, 디-알레이트, 디메피페레이트, EPTC, 에스프로카르브, 몰리네이트, 페불레이트, 프로술포카르브, 티오벤카브 (벤티오카브), 트리-알레이트 또는 베르놀레이트, 벤푸레세이트 또는 퍼플루이돈을 사용할 수 있다.Examples of the lipid biosynthesis inhibitor include anilope or mefenacet as anilide, dimethanamide, S-dimethenamid, acetochlor, alachlor, butachlor, butenachlor, diethylacetyl, Propyl chloro, perchloro, terbuchlor, decyl chlor or xyl chlor, thiourea, butyrate, cyclohexyl, di-tert-butyl, But are not limited to, allyl, dimepiperate, EPTC, escocarb, molinate, peburate, prosulfocarb, thiobenzoc (benthiocarb), tri- Can be used.

상기 유사분열 억제제로는 카르바메이트로서 아술람, 카르베타미드, 클로르프로팜, 오르벤카르브, 프론아미드 (프로피자미드), 프로팜 또는 티오카르바질, 디니트로아닐린로서 베네핀, 부트랄린, 디니트라민, 에탈플루랄린, 플루클로랄린, 오리잘린, 펜디메탈린, 프로디아민 또는 트리플루랄린, 피리딘으로서 디티오피르 또는 티아조피르, 부타미포스, 클로르탈-디메틸 (DCPA) 또는 말레산 히드라지드를 사용할 수 있다.Examples of the mitotic inhibitor include carbamates such as asulam, carbethamide, chlorpropam, orbencarb, pranamide (propizamide), propham or thiocarbazil, venin as denitroaniline, butralin (DCPA) or maleic anhydride such as dithiopyr or thiazopyr, butamiphor, chlortal-dimethyl (DCPA) or malefurane as the pyridine, pyrimidine, pyrimidine, Acid hydrazide can be used.

상기 프로토포르피리노겐 IX 옥시다제 억제제는 다이페닐 에테르로서 아시플루오르펜, 아시플루오르펜-나트륨, 아클로니펜, 비페녹스, 클로르니트로펜 (CNP), 에톡시펜, 플루오로디펜, 플루오로글리코펜-에틸, 포메사펜, 푸릴옥시펜, 락토펜, 니트로펜, 니트로플루오르펜 또는 옥시플루오르펜, 옥사다이아졸로서 옥사디아르길 또는 옥사디아존, 사이클릭 이미드로서 아자페니딘, 부타펜아실, 카르펜트라존-에틸, 시니돈-에틸, 플루미클로락-펜틸, 플루미옥사진, 플루미프로핀, 플루프로파실, 플루티아세트-메틸, 술펜트라존 또는 티디아지민, 피라졸로서 피라플루펜-에틸을 사용할 수 있다.  Wherein the protoporphyrinogen IX oxidase inhibitor is selected from the group consisting of acifluorfen, acifluorfen-sodium, aclionfen, bifenox, chlorinitrophen (CNP), ethoxyphene, fluorodiphen, fluoroglycophene - oxadiazole or oxadiazon as the oxadiazole, azaphenidine, butaphenacyl, isophenoxyphenyl, cyclopentadienyl, cyclopentadienyl, cyclopentadienyl, But are not limited to, carfentrazone-ethyl, cinidon-ethyl, cinidon-ethyl, flimiclolac-pentyl, flumioxam, flumipropin, flupropacil, fluthiacet-methyl, sulfentrazone or thidiazimine, Pen-ethyl can be used.

상기 광합성 억제제는 프로파닐, 피리데이트 피리다폴, 벤조티아디아지논으로서 벤타존, 디니트로페놀으로서 브로모페녹심, 디노셉, 디노셉-아세테이트, 디노테르브 또는 DNOC, 디피리딜렌으로서 시페르쿼트-클로라이드, 디펜조쿼트-메틸술페이트, 디쿼트 또는 파라쿼트-디클로라이드, 우레아로서 클로르브로무론, 클로로톨루론, 디페녹수론, 디메푸론, 디우론, 에티디무론, 페누론, 플루오메투론, 이소프로투론, 이소우론, 리누론, 메타벤즈티아주론, 메타졸, 메토벤주론, 메톡수론, 모노리누론, 네부론, 시두론 또는 테부티우론, 페놀로서 브로목시닐 또는 이옥시닐, 클로리다존, 트리아진으로서 아메트린, 아트라진, 시아나진, 데스메트린, 디메타메트린, 헥사지논, 프로메톤, 프로메트린, 프로파진, 시마진, 시메트린, 테르부메톤, 테르부트린, 테르부틸아진 또는 트리에타진, 트리아지논으로서 메타미트론 또는 메트리부진, 우라실으로서 브로마실, 레나실 또는 테르바실, 비스카르바메이트로서 데스메디팜 또는 펜메디팜을 사용할 수 있다.The photosynthesis inhibitor may be selected from the group consisting of propanil, pyridate pyridapol, benzazone as benzothiadiazinone, bromophenoxime as dinitrophenol, dinoseph, dinoseph-acetate, dinotereb or DNOC, Dichloromethane, dichloromethane, chloroform, diphenoquat-methyl sulfate, diquat or paraquat-dichloride as urea, chlorobromuron as urea, chlorotoluron, diphenoxuron, dimerpuron, diuron, ethidimuron, peruron, But are not limited to, prothuron, isoron, lenuron, meta benzothiazuron, metazoles, metobenzuron, methoxuron, monolinuron, neburon, syduron or tebuturon, bromosininyl or dioxinyl as phenol, Atrazine, cyanazine, desmethrin, dimethmethrin, hexazinone, promethone, promethrin, propazine, simazine, imatinine, terbumethone, terbutaline , Terbutyl Azine or triazinone, metamitron or metrizin as the triazinone, bromacil, renasil or tervacil as uracil, desmedipham or penemedipam as the biscarbamate.

상기 상승작용제로는 옥시란으로서 트리디판을 사용할 수 있고, 상기 성장 물질로는 아릴옥시알칸산으로서 2,4-DB, 클로메프로프, 디클로르프로프, 디클로르프로프-P(2,4-DP-P), 플루오르옥시피르, MCPA, MCPB, 메코프로프, 메코프로프-P 또는 트리클로피르, 벤조산으로서 클로르암벤 또는 디캄바, 퀴놀린카르복실산으로서 퀸클로락 또는 퀸메락을 사용할 수 있으며 상기 세포벽 합성 억제제 이속사벤 또는 디클로베닐을 사용할 수 있다. As the synergist, tridiphenyl may be used as oxirane. Examples of the growth material include 2,4-DB, clemeproof, dichlorpropop, dichlorprop-P (2,4 -DP-P), fluoroxypyr, MCPA, MCPB, methoprotein, methoproph-P or trichlorpyrone, chlorobenzene or dicamba as benzoic acid, quinclorac or quinmalac as quinolinecarboxylic acid The cell wall synthesis inhibitor isoxane or dicarbonyl may be used.

상기 기타 제초제로는 다이클로로프로피온산으로서 달라폰, 다이히드로벤조푸란으로서 에토푸메세이트, 페닐아세트산으로서 클로르페낙(페낙), 또는 아지프로트린, 바르반, 벤술리드, 벤즈티아주론, 벤조플루오르, 부미나포스, 부티다졸, 부투론, 카펜스트롤, 클로르부팜, 클로르펜프로프-메틸, 클로르옥수론, 신메틸린, 쿠밀루론, 사이클루론, 시프라진, 시프라졸, 디벤질루론, 디프로페트린, 딤론, 에글리나진-에틸, 엔도탈, 에티오진, 플루카바존, 플루오르벤트라닐, 플루폭삼, 이소카르바미드, 이소프로팔린, 카르부틸레이트, 메플루이디드, 모누론, 나프로파미드, 나프로파닐리드, 니트랄린, 옥사사이클로메폰, 페니소팜, 피페로포스, 프로시아진, 프로플루랄린, 피리부티카르브, 섹부메톤, 술팔레이트(CDEC), 테르부카르브, 트리아지플람, 트리아펜아미드 또는 트리메투론 및 이들의 환경친화적 염을 사용할 수 있다.Examples of the other herbicide include daphenone as dichloropropionic acid, ethofumesate as dihydrobenzofuran, chlorphenacin (phenac) as phenylacetic acid, or azeprotrine, barbane, benzylide, benzthiazuron, benzofluor, But are not limited to, minipos, butyridazole, butyrone, carpentrol, chlorpublam, chlorfenprop-methyl, chloroxalone, neomethyline, cumyluron, cyclolone, cyprazine, ciprazole, dibenzyluron, But are not limited to, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, (CDEC), terbuticarb, triacetin, tetracycline, propylglycine, propylglycine, propylglycine, propylglycine, Aziplam, triaphenia Or a de-trimethoxy Turone and their salts may be environmental friendly.

본 발명에 따른 화합물은 유해 식물에 대해 제초 활성을 갖는다. 상기 '유해 식물'은 농작물 경작지에서 자라는 원하지 않는 식물로, 방제가 필요한 식물을 일컫는다. 잡초는 그 수가 매우 많고, 분류방법도 매우 다양하다. The compounds according to the invention have herbicidal activity against harmful plants. The 'harmful plant' is an unwanted plant that grows in the cultivation area of the crop, and refers to a plant that needs to be controlled. The number of weeds is very large, and classification methods are very diverse.

통상적인 잡초 분류방법으로서 형태에 따라 화본과 잡초, 사초과 잡초, 광엽 잡초로 분류하기도 한다. 상기 화본과 잡초는 수수, 돌피, 개밀, 미국개기장, 바랭이, 민바랭이, 왕바랭이, 강아지풀, 수강아지풀, 가을강아지풀, 드렁새, 비노리, 큰비노리, 가락지조, 포아풀 또는 왕포아풀 등이 포함된다. 상기 사초과 잡초는 금방동사니, 올챙이고랭이, 향부자, 너도방동사니, 쇠털골, 올방개, 매자기 등이 포함된다. 상기 광엽 잡초는 물달개비, 까마중, 도꼬마리 등이 포함된다.It is classified into weeds, weeds, weeds, weeds and light weeds. The handwritings and weeds include, but are not limited to, millet, cormorant, cormorant, american cormorant, barnacles, mackerel, king mackerel, mackerel, mackerel, autumn mackerel, mackerel, mackerel, mackerel, mackerel, and pineapple. The above-mentioned grasses and weeds include gold-tinted gulls, tadpole gulls, herbal tortoises, buccal tortoises, buccal stones, The light leaf weeds include water tannin, ragweed, horse mackerel and the like.

또한, 잡초의 엽수에 따라 단자엽 또는 쌍자엽 잡초로 분류하기도 한다. 단자엽 잡초 종으로는 화본과 잡초 또는 사초과 잡초가 포함될 수 있다. 쌍자엽 잡초 종으로는 한련초, 털진득찰, 중대가리풀, 개쑥갓, 쑥, 미국가막사리, 서양민들레, 개망초, 망초, 털별꽃아재비, 지칭개, 보리뺑이, 사철쑥, 도깨비바늘, 진득찰, 단풍잎돼지풀, 씀바귀, 고들빼기, 왕고들빼기, 미국쑥부쟁이, 조뱅이, 민들레, 돼지풀, 뚱딴지, 붉은서나물 등의 국화과 잡초; 향유, 석잠풀, 들깨풀, 익모초 등의 꿀풀과 잡초; 깨풀, 큰땅빈대, 애기땅빈대 등의 대극과 잡초; 주름잎, 밭뚝외풀 등의 현삼과 잡초; 까마중, 미국까마중 등의 가지과 잡초; 개비름, 가는털비름 등의 비름과 잡초; 괭이밥, 선괭이밥 등의 괭이밥과 잡초; 유럽쥐손이풀, 이질풀 등의 쥐손이풀과 잡초; 수박풀, 어저귀 등의 아욱과 잡초; 환삼덩굴, 삼 등의 삼과 잡초; 여뀌바늘, 겹달맞이꽃 등의 바늘꽃과 잡초; 쇠비름 등의 쇠비름과 잡초; 쇠뜨기 등의 속새과 잡초; 반하 등의 천남성과 잡초; 사상자 등의 산형과 잡초; 석류풀 등의 석류풀과 잡초; 닭의장풀 등의 닭의장풀과 잡초; 돌나물 등의 돌나물과 잡초; 애기똥풀 등의 양귀비과 잡초; 박주가리 등의 박주가리과 잡초; 제비꽃 등의 제비꽃과 잡초; 쇠별꽃 등의 석죽과 잡초; 모시물통이 등의 쐐기풀과 잡초; 꽃마리 등의 지치과 잡초; 질경이 등의 질경이과 잡초; 개소시랑개비 등의 장미과 잡초; 물달개비 등의 물옥잠과 잡초 등이 포함될 수 있다.Depending on the number of leaves of the weeds, they may be classified as terminal or dicotyledonous weeds. Monocotyledonous weed species may include weeds and weeds or strata and weeds. Dicotyledonous weeds species include, but are not limited to, hanwonchu, firestone, giant clam, mugwort, mugwort, american mangrove, dandelion, amphibian, mangrove, Chrysanthemums and weeds, such as stinks, rhizomes, kangaroos, american grasshoppers, dandelions, dandelions, pig grass, Lamiaceae and weeds such as perfume, persimmon grass, perilla grass, motherwort; Countermeasures and weeds such as Nipponbuga, Nipponbugi, Nipponbugi, and others; Wrinkled leaves, weeds such as mulberry leaves and weeds; Branches and weeds in the grass; Weeping and Weeping; Oxalate and weeds such as oxalic acid, and oxalic acid; Rusty weeds and weeds, such as European mussel, mussel; Watermelon grass, weevil and other weevils; Weed, weed; Needles and weeds such as needles, double-evening primrose; Leggings and weeds; Horses and weeds; Weed and weed; Mountain types and weeds such as casualties; Pomegranate grass and weeds such as pomegranate grass; Chicken foxtail and weeds such as chicken foxtail; Sedge and weeds; Poppy and weed; Pusan and weeds such as pusan; Violets and weeds; Ginseng and weeds; Nettle and weed of ramie buckets; Weeds, such as flowers; Plantain and weeds such as plantain; Rosaceae weeds such as spotted cranberries; Water weeds, weeds, and the like.

[실험예][Experimental Example]

다음은 본 발명의 화합물들이 나타내는 잡초방제 효과를 실험한 예이다.
The following are examples of the weed control effect of the compounds of the present invention.

실험예 1. 수면처리 실험 EXPERIMENTAL EXAMPLE 1

체(sieve)로 쳐서 보관된 논흙을 교반기에 넣어 물을 공급하면서 섞어 곤죽이 되도록 하였고, 토양 2 kg당 수도용 복합비료(N-P-K : 21-17-17)가 1 g씩 들어가도록 섞어주었다. 토양 중에 혼입된 종자와 토양 미생물에 의한 실험상의 오차를 방지하기 위해 120℃에서 30분간 토양 멸균기에서 증기 멸균하여 사용하였다. The soil mixed with sieve was put into a stirrer and mixed with water to make a puddle. 1 kg of mixed fertilizer (N-P-K: 21-17-17) was mixed per 2 kg of soil. In order to prevent experimental errors caused by the seeds and soil microorganisms in the soil, they were steam sterilized in a soil sterilizer for 30 minutes at 120 ° C.

파종은, 논 흙 표면을 고르게 편 후 적당량의 종자를 적절한 위치에 뿌려주고, 흙 속으로 묻힐 수 있도록 눌러 주었다. 물달개비 (M. vaginalis), 올챙이고랭이 (S. juncoides)는 2 mm 이내 정도에 묻히게 하였고, 피는 1 cm 이상 묻어 주어 발아시 물에 뜨지 않도록 하였다. 파종후 2~3일 내에 2 엽기의 벼를 포트당 2개씩 이앙하였다.Sowing was done by evenly spreading the surface of the paddy soil, spraying an appropriate amount of seeds to the proper position, and pressing them to be buried in the soil. M. vaginalis and tadpole S. juncoides were allowed to bury within 2 mm, and blooms were buried more than 1 cm to prevent them from floating on germination. Within two to three days after sowing, two leaves were transferred per pot.

약제처리는 벼 이앙 후 15일경에, 소요 원제량에 최종 조제액이 트윈 (Tween) 20 0.2%, 아세톤 50%, 물 50%가 되도록 조제하였다. 활성화합물의 양은 원하는 특정 량이 되도록 선택하였다.In the chemical treatment, about 15 days after the transplanting of rice, the final preparation liquid was adjusted to 0.2% Tween 20, 50% acetone, and 50% water in the required amount of the raw material. The amount of active compound was selected to be the desired specific amount.

약제처리 후 온실조건(주간온도 25∼35℃/야간온도 20∼25℃, 14시간 광주기)에서 2주 동안 생육시킨 다음, 각 식물에 대한 제초활성을 잡초에 대해서는 0(무방제) ∼ 100(완전방제), 작물에는 0(무해) ∼ 10(완전고사) 등급표에 준하여 달관 조사하여 무 처리구에 대한 방제가로 평가하였다.
The herbicidal activity of each plant was evaluated as 0 (no protection) to 100 (weight loss) for the weeds after 2 weeks of growth in the greenhouse condition (day temperature 25 ~ 35 ℃ / night temperature 20 ~ 25 ℃, (Complete control), and the crops were evaluated by 0 to 10 (complete score) grades according to the rating table.

실험예 2 : 경엽처리 실험Experimental Example 2: Foliar treatment experiment

경엽처리는 표면적 350 cm2 사각플라스틱 포트에 원예용 상토를 충진하였다. 그리고, 저온고 (6 ℃)에 보관중인 바랭이, 수수, 돌피 3종의 화본과 잡초 및 까마중, 도꼬마리 2종의 광엽 잡초의 종자 (10~15립), 지하경 (2개체) 및 벼를 파종하였다. 온실조건 (평균 온도 30ㅁ5℃, 광/암=14/10시간)에서 일정기간 생육시킨 후, 실험화합물 최종 처리량을 75 g a.i./ha양이 되도록 희석제 (50% 아세톤, Tween-20 0.1% 포함)로 희석하여 실험화합물 용액을 조제하였다. 조제된 실험화합물 용액을 포트 당 14 mL 량으로 흄 후드 내에서 핸드 스프레이를 이용하여 경엽처리하였다. 상기와 동일한 온실조건에서 관리하였고, 7일 및 14일 후(필요 시 21일 후)에 외형적인 증상 및 약효/약해를 잡초에 대해서는 0(무방제) ∼ 100(완전방제), 작물에는 0(무해) ∼ 10(완전고사) 등급표에 준하여 달관 조사하여 무 처리구에 대한 방제가로 평가하였다. The foliar treatment was filled with horticultural soil on a square plastic port with a surface area of 350 cm 2 . Then seeds (10 ~ 15 lips), subterranean trees (2 plants) and rice were sown in the weeds and weeds and weeds and two weeds of two species of weevil, which were kept at low temperature (6 ℃). (50% acetone, 0.1% Tween-20) to a final amount of 75 g ai / ha of the experimental compound after a certain period of growth in a greenhouse condition (average temperature 30 ㅁ 5 ° C, light / ) To prepare an experimental compound solution. The prepared test compound solution was subjected to foliar treatment using hand spray in a fume hood at a volume of 14 mL per pot. (Symptomatic and medicinal / phytotoxic) on days 7 and 14 (after 21 days if necessary) were controlled to 0 (no protection) to 100 (complete control) for weeds and 0 (Harmless) to 10 (complete test) grade.

또한, 본 실험에서는 대조화합물로서 특허문헌 1(국제공개특허공보 WO2003-066607호)에 개시된 화합물을 사용하였으며, 대조화합물 1과 2의 화학구조는 하기와 같다.In this experiment, the compound disclosed in Patent Document 1 (International Patent Publication No. WO2003-066607) was used as a control compound, and the chemical structures of Control Compounds 1 and 2 were as follows.

[대조화합물 1][Control Compound 1]

Figure pat00036
Figure pat00036

[대조화합물 2][Control Compound 2]

Figure pat00037

Figure pat00037

본 발명의 화합물에 대해 수면처리 실험한 결과는 하기 표 4에 나타내었고 경엽처리 실험한 결과는 하기 표 5에 나타내었다. The results of the sleep treatment of the compound of the present invention are shown in the following Table 4 and the results of the foliar treatment test are shown in Table 5 below.

수면처리 제초 활성시험 (200g a.i./ha)Sleeping herbicidal activity test (200g a.i./ha) 실험화합물Experimental compound 잡초weed 작물crops 물달개비Water tiller 올챙이고랭이Tadpole 벼rice plant 화합물번호 2Compound No. 2 9999 8888 -- 화합물번호 4Compound No. 4 9797 7575 -- 화합물번호 7Compound No. 7 100100 9595 -- 화합물번호 9Compound No. 9 100100 9090 0.00.0 화합물번호 12Compound No. 12 9797 8080 -- 화합물번호 27Compound No. 27 9797 7575 0.00.0 화합물번호 32Compound No. 32 100100 7575 -- 화합물번호 35Compound No. 35 9797 8585 0.00.0 대조화합물 1Control Compound 1 9797 6565 3.03.0 대조화합물 2Control Compound 2 100100 9090 3.03.0

상기 표 4의 수면처리 제초활성 시험결과에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 물달개비, 올챙이고랭이와 같은 난방제 논 잡초를 방제하는 효과가 탁월하였다. 또한, 제초활성이 우수한 것으로 확인되고 있는 화합물번호 9, 27 및 35의 화합물과 대조화합물 1 및 2에 대하여 작물 약해실험을 실시한 결과가 상기 표 4에 기재되어 있다. 상기 표 4에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 벼에 대한 높은 안전성을 나타냄을 확인할 수 있다.
According to the results of the water treatment herbicidal activity test of Table 4, the compound represented by Formula 1 according to the present invention has excellent effect of controlling the weeds of heating agents such as water falciparum and tadpole gourd. In addition, the results of crop tolerance tests on the compounds of Compound Nos. 9, 27 and 35 and Comparative Compounds 1 and 2, which have been confirmed to have excellent herbicidal activity, are shown in Table 4 above. According to the above Table 4, it can be confirmed that the compound represented by Formula 1 according to the present invention shows high safety against rice.

경엽처리 제초 활성시험 (75g a.i./ha)Herbicidal activity test (75g a.i./ha) 실험화합물Experimental compound 잡초weed 작물crops 수수Sorghum 돌피Peck 바랭이wire grass 까마중Mad 도꼬마리A toddler 벼rice plant 화합물번호 41Compound No. 41 9595 9898 9898 100100 100100 -- 화합물번호 44Compound No. 44 7070 9595 7070 100100 9898 0.00.0 화합물번호 48Compound No. 48 7070 9898 8080 100100 9898 0.00.0 화합물번호 61Compound No. 61 8080 9595 9090 100100 9898 0.00.0 화합물번호 62Compound No. 62 9898 9898 100100 100100 9898 0.00.0 화합물번호 63Compound No. 63 100100 9898 9898 100100 9898 -- 화합물번호 67Compound No. 67 9898 9595 9595 100100 9898 0.00.0 화합물번호 68Compound No. 68 9898 9898 9898 100100 9898 0.00.0 화합물번호 69Compound No. 69 9090 9595 9595 100100 9898 -- 화합물번호 70Compound No. 70 9898 9898 9898 100100 100100 0.00.0 화합물번호 71Compound No. 71 8080 9595 9595 100100 9090 -- 화합물번호 91Compound No. 91 9898 9595 9898 100100 9898 0.00.0 화합물번호 94Compound No. 94 9898 9595 9898 100100 9898 -- 화합물번호 96Compound No. 96 9898 9898 100100 100100 9898 -- 화합물번호 101Compound No. 101 9898 100100 100100 100100 9898 -- 화합물번호 104Compound No. 104 7070 9898 8080 100100 9898 0.00.0 화합물번호 118Compound No. 118 9898 9898 9595 100100 9898 -- 화합물번호 119Compound No. 119 9898 9595 9898 100100 9898 -- 화합물번호 120Compound No. 120 8080 9595 9090 100100 9595 -- 화합물번호 121Compound No. 121 9595 9898 7070 100100 9090 -- 화합물번호 123Compound No. 123 9595 9898 100100 100100 9898 -- 화합물번호 124Compound No. 124 100100 9898 9898 100100 9898 -- 화합물번호 125Compound No. 125 100100 9898 9898 9898 9595 -- 화합물번호 133Compound No. 133 100100 9898 9898 100100 9898 -- 화합물번호 135Compound No. 135 100100 9595 9898 100100 9090 -- 화합물번호 136Compound No. 136 100100 9898 9898 100100 8080 -- 대조화합물 1Control Compound 1 4040 9595 6060 9898 9595 3.03.0 대조화합물 2Control Compound 2 9595 9898 9595 9595 8080 5.05.0

상기 표 5의 경엽처리 제초활성 시험결과에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 수수, 돌피, 바랭이, 까마중, 도꼬마리와 같은 잡초를 방제하는 효과가 탁월하였다. 또한, 제초활성이 우수한 것으로 확인되고 있는 화합물번호 44, 48, 61, 62, 67, 68, 70, 91, 104의 화합물과 대조화합물 1 및 2에 대하여 작물 약해실험을 실시한 결과가 상기 표 5에 기재되어 있다. 상기 표 5에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 벼에 대한 높은 안전성을 나타냄을 확인할 수 있다. According to the results of the herbicidal herbicidal activity test of Table 5, the compound of Formula 1 according to the present invention was excellent in controlling weeds such as sorghum, horseshoe, lettuce, and weed. In addition, the results of the crop tolerance test on the compounds of Compound Nos. 44, 48, 61, 62, 67, 68, 70, 91 and 104 and the Control Compounds 1 and 2, . According to the above Table 5, it can be confirmed that the compound represented by Formula 1 according to the present invention shows high safety for rice.

Claims (17)

하기 화학식 1로 표시되는 벤조일사이클로헥사다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 화합물 :
[화학식 1]
Figure pat00038

상기 화학식 1에서,
R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1∼C6알킬) 를 나타내고;
R2 및 R3은 각각 독립적으로 수소원자, 또는 C1∼C6알킬기를 나타내고;
R4는 -C1∼C6알킬렌-, -C2∼C6알케닐렌-, -C2∼C6알키닐렌-, C1∼C6할로알킬렌기, -(C1∼C6알킬렌)-O-(C1∼C6알킬렌)-, 또는 -(C1∼C6알킬렌)-S-(C1∼C6알킬렌)-를 나타내고;
X는 할로젠원자, 또는 C1∼C6알킬기를 나타내고;
Y는 -NO2, 또는 -S(O)2-(C1∼C2알킬)를 나타내고;
Z는
Figure pat00039
,
Figure pat00040
또는
Figure pat00041
로부터 선택되고,
R5는 수소원자, 할로젠원자, C1∼C6알킬기, 또는 C1∼C6할로알킬기를 나타내고;
n은 0, 1, 또는 2의 정수를 나타낸다.
A compound selected from the group consisting of benzoylcyclohexadarone compounds represented by the following formula (1) and pesticidally acceptable salts thereof:
[Chemical Formula 1]
Figure pat00038

In Formula 1,
R 1 represents a halogen atom, a hydroxyl group, or -OC (O) - (C 1 -C 6 alkyl);
R 2 and R 3 are each independently a hydrogen atom or a C 1 -C 6 alkyl group;
R 4 is -C 1 -C 6 alkylene-, -C 2 -C 6 alkenylene-, -C 2 -C 6 alkynylene-, C 1 -C 6 haloalkylene group, - (C 1 -C 6 alkyl alkylene) -O- (C 1 ~C 6 alkylene) -, or - (C 1 ~C 6 alkylene) -S- (C 1 ~C 6 alkylene) - represents;
X represents a halogen atom, or a C 1 -C 6 alkyl group;
Y represents -NO 2 , or -S (O) 2 - (C 1 -C 2 alkyl);
Z is
Figure pat00039
,
Figure pat00040
or
Figure pat00041
≪ / RTI >
R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, or a C 1 -C 6 haloalkyl group;
n represents an integer of 0, 1, or 2;
제 1 항에 있어서,
상기 R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1∼C4알킬)를 나타내고;
상기 R2 및 R3은 각각 독립적으로 수소원자, 메틸기, 에틸기, 노말프로필기, 또는 이소프로필기를 나타내고;
상기 R4는 -C1∼C4알킬렌-, -C2∼C4알케닐렌-, -C2∼C4알키닐렌-, -C1∼C4할로알킬렌-, -(C1∼C4알킬렌)-O-CH2-, -(C1∼C4알킬렌)-O-CH2CH2-, -(C1∼C4알킬렌)-S-CH2-, 또는 -(C1∼C4알킬렌)-S-CH2CH2- 를 나타내고;
상기 X는 할로젠원자, 또는 C1∼C4알킬기를 나타내고;
상기 Y는 -NO2, 또는 -S(O)2-CH3 를 나타내고;
상기 Z는
Figure pat00042
,
Figure pat00043
또는
Figure pat00044
로부터 선택되고,
상기 R5는 수소원자, 할로젠원자, C1∼C4알킬기, 또는 C1∼C4할로알킬기를 나타내고;
상기 n은 0, 1, 또는 2의 정수를 나타내는 것을 특징으로 하는 화합물.
The method according to claim 1,
Wherein R 1 represents a halogen atom, a hydroxy group, or -OC (O) - (C 1 -C 4 alkyl);
Each of R 2 and R 3 independently represents a hydrogen atom, a methyl group, an ethyl group, a normal propyl group or an isopropyl group;
Wherein R 4 is -C 1 ~C 4 alkylene -, -C 2 ~C 4 alkenylene -, -C 2 ~C 4 alkynylene -, -C 1 ~C 4 haloalkyl alkylene -, - (C 1 ~ C 4 alkylene) -O-CH 2 -, - (C 1 ~C 4 alkylene) -O-CH 2 CH 2 - , - (C 1 ~C 4 alkylene) -S-CH 2 -, or - (C 1 -C 4 alkylene) -S-CH 2 CH 2 -;
X represents a halogen atom, or a C 1 -C 4 alkyl group;
Wherein Y is -NO 2, Or -S (O) -CH 3 represents a 2;
Z is
Figure pat00042
,
Figure pat00043
or
Figure pat00044
≪ / RTI >
R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, or a C 1 -C 4 haloalkyl group;
And n represents an integer of 0, 1, or 2.
제 1 항에 있어서,
상기 R1은 클로로원자, 하이드록시기, 또는 -O-C(O)-(C1∼C4알킬)를 나타내고;
상기 R2 및 R3은 각각 독립적으로 수소원자, 또는 메틸기를 나타내고;
상기 R4는 -C1∼C4알킬렌-, -C2∼C4알케닐렌-, -C2∼C4알키닐렌-, -C1∼C2할로알킬렌-, -(C1∼C2알킬렌)-O-CH2-, -(C1∼C2알킬렌)-O-CH2CH2-, -(C1∼C2알킬렌)-S-CH2-, 또는 -(C1∼C2알킬렌)-S-CH2CH2- 를 나타내고;
상기 X는 클로로원자, 또는 메틸기를 나타내고;
상기 Y는 -NO2, 또는 -S(O)2-CH3를 나타내고;
상기 Z는
Figure pat00045
,
Figure pat00046
,
Figure pat00047
,
Figure pat00048
,
Figure pat00049
, 또는
Figure pat00050
를 나타내고;
상기 n은 0, 또는 2의 정수를 나타내는 것을 특징으로 하는 화합물.
The method according to claim 1,
Wherein R 1 represents a chloro atom, a hydroxy group, or -OC (O) - (C 1 -C 4 alkyl);
Each of R 2 and R 3 independently represents a hydrogen atom or a methyl group;
Wherein R 4 is -C 1 ~C 4 alkylene -, -C 2 ~C 4 alkenylene -, -C 2 ~C 4 alkynylene -, -C 1 ~C 2 haloalkoxy alkylene -, - (C 1 ~ C 2 alkylene) -O-CH 2 -, - (C 1 ~C 2 alkylene) -O-CH 2 CH 2 - , - (C 1 ~C 2 alkylene) -S-CH 2 -, or - (C 1 -C 2 alkylene) -S-CH 2 CH 2 -;
X represents a chloro atom, or a methyl group;
Wherein Y is -NO 2, Or -S (O) -CH 3 represents a 2;
Z is
Figure pat00045
,
Figure pat00046
,
Figure pat00047
,
Figure pat00048
,
Figure pat00049
, or
Figure pat00050
Lt; / RTI >
Wherein n represents an integer of 0 or 2.
제 1 항에 있어서,
상기 R1은 클로로원자, 하이드록시기, 또는 -O-C(O)-(C1∼C4알킬)를 나타내고;
상기 R2 및 R3은 각각 독립적으로 수소원자, 또는 메틸기를 나타내고;
상기 R4는 -CH2-, -(CH2)2-, -(CH2)3-, -CH2CH(CH3)-, -(CH2)4-, -CH2CH(CH3)CH2-, -(CH2)5-, -CH2C(CH3)2CH2-, cis -CH2CH=CHCH2-, trans -CH2CH=CHCH2-, -CH2C≡CCH2-, -CH2CHF-, -CH2-O-CH2-, -(CH2)2-O-CH2-, -CH2-O-(CH2)2-, -(CH2)2-O-(CH2)2-, -CH2-S-CH2-, -(CH2)2-S-CH2-, -CH2-S-(CH2)2-, 또는 -(CH2)2-S-(CH2)2-를 나타내고;
상기 X는 클로로원자, 또는 메틸기를 나타내고;
상기 Y는 -NO2, 또는 -S(O)2-CH3를 나타내고;
상기 Z는
Figure pat00051
,
Figure pat00052
또는
Figure pat00053
를 나타내고;
상기 n은 0, 또는 2의 정수를 나타내는 것을 특징으로 하는 화합물. The method according to claim 1,
Wherein R 1 represents a chloro atom, a hydroxy group, or -OC (O) - (C 1 -C 4 alkyl);
The R 2 And R 3 each independently represent a hydrogen atom or a methyl group;
Wherein R 4 is -CH 2 -, - (CH 2 ) 2 -, - (CH 2) 3 -, -CH 2 CH (CH 3) -, - (CH 2) 4 -, -CH 2 CH (CH 3 ) CH 2 -, - (CH 2) 5 -, -CH 2 C (CH 3) 2 CH 2 -, cis -CH 2 CH = CHCH 2 -, trans -CH 2 CH = CHCH 2 -, -CH 2 C ≡CCH 2 -, -CH 2 CHF-, -CH 2 -O-CH 2 -, - (CH 2) 2 -O-CH 2 -, -CH 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -, -CH 2 -S-CH 2 -, - (CH 2) 2 -S-CH 2 -, -CH 2 -S- (CH 2) 2 -, or - (CH 2 ) 2 -S- (CH 2 ) 2 -;
X represents a chloro atom, or a methyl group;
Wherein Y is -NO 2, Or -S (O) -CH 3 represents a 2;
Z is
Figure pat00051
,
Figure pat00052
or
Figure pat00053
Lt; / RTI >
Wherein n represents an integer of 0 or 2. 제 1 항에 있어서,
2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 2);
2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 4);
2-(3-(2-(1H-1,2,3-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 7);
2-(3-(4-(1H-1,2,3-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 9);
2-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 12);
3-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 27);
2-(3-(2-(3-브로모-1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 32);
2-(3-(2-((1H-1,2,3-트리아졸-1-일)메톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 35);
2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 41);
2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 44);
2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 48);
3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 61);
3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 아세테이트 (화합물번호 62);
3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 사이클로프로판카르복실레이트 (화합물번호 63);
2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 67);
2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 사이클로프로판카르복실레이트 (화합물번호 68);
2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아이소부티레이트 (화합물번호 69);
2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 피발레이트 (화합물번호 70);
2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 71);
2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 91);
3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 94);
3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 96);
2-(3-(2-(1H-1,2,3-트리아졸-1-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 101);
2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아이소부티레이트 (화합물번호 104);
2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-플루오로사이클로헥-2-센-1-온 (화합물번호 118);
2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-브로모사이클로헥-2-센-1-온 (화합물번호 119);
2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 120);
2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 121);
2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 123);
2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 124);
2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온(화합물번호 125);
3-클로로-2-(3-(2-플루오로-2-(1H-1,2,3-트리아졸-1-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)사이클로헥-2-센-1-온 (화합물번호 133);
3-클로로-2-(3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)사이클로헥-2-센-1-온 (화합물번호 135);
2-(3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 136); 및
농약학적으로 허용 가능한 이들의 염으로 이루어진 군으로부터 선택된 화합물.
The method according to claim 1,
2- (3- (2- (2 H- 1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 2);
2- (3- (4- (2 H- 1,2,3- triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 4);
2- (3- (2- (1 H- 1,2,3- triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 7);
2- (3- (4- (1 H- 1,2,3- triazol-1-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 9);
2- (3- (2- (1 H- 1,2,4- triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 12);
3- (3- (2- (1 H- 1,2,4- triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4-hydroxy-bicyclo [ 3.2.1] ox-3-en-2-one (Compound No. 27);
() -2-chloro-4- (methylsulfonyl) 3- (2- (3-bromo -1 H -1,2,4- triazol-1-yl) benzoyl) -3-2- 2-en-1-one (Compound No. 32);
2- (3- (2 - (( 1 H- 1,2,3- triazol-1-yl) methoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxy 2-en-1-one (Compound No. 35);
2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydroxy-cyclohexyl- 2-en-1-one (Compound No. 41);
2- (3- (2- (2 H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoyl) -3-hydroxycyclohexyl- One (Compound No. 44);
2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) Benzoyl) -3-hydroxycyclohexyl-2-en-1-one (Compound No. 48);
() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 - hydroxybicyclo [3.2.1] oct-3-en-2-one (Compound No. 61);
() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 - oxobicyclo [3.2.1] oct-2-yl-2-yl acetate (Compound No. 62);
() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 -Oxobicyclo [3.2.1] oct-2-yl) -2-ylcyclopropanecarboxylate (Compound No. 63);
(3-ethoxy (ethoxy-2- (2 H -1,2,3- triazol-2-yl))) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo Hept-1-en-1-yl acetate (Compound No. 67);
(3-ethoxy (ethoxy-2- (2 H -1,2,3- triazol-2-yl))) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo Hex-1-en-1-yl cyclopropanecarboxylate (Compound No. 68);
(3-ethoxy (ethoxy-2- (2 H -1,2,3- triazol-2-yl))) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo 1-en-1-ylisobutyrate (Compound No. 69);
(3-ethoxy (ethoxy-2- (2 H -1,2,3- triazol-2-yl))) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo Hex-1-sen-1-yl pivalate (Compound No. 70);
2- (3- (2- (2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-cyclohexyl -1 -Acen-1-yl acetate (Compound No. 71);
() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 2-3 -Cyclohex-2-en-1-one (Compound No. 91);
() -2-chloro-4- (methylsulfonyl) 3- (2- (2- (2 H -1,2,3- triazol-2-yl)) benzoyl) 3-4 -Chlorobiscyclo [3.2.1] oct-3-en-2-one (Compound No. 94);
3- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -4-chloro-by Cyclo [3.2.1] ox-3-en-2-one (Compound No. 96);
(Ethoxy-3- (2- (1 H -1,2,3- triazol-1-yl) ethoxy)) 2-chloro-4- (methylsulfonyl) 2-benzoyl) -3-oxo-bicyclo Hept-1-en-1-yl acetate (Compound No. 101);
2- (3 - ((4- (2 H -1,2,3-triazol-2-yl) Benzoyl) -3-oxocyclohexyl-1-sen-1-ylisobutyrate (Compound No. 104);
2- (3- (3- (2 H -1,2,3- triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-fluoro-cyclohexyl- 2-en-1-one (Compound No. 118);
2- (3- (3- (2 H -1,2,3- triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-bromo-cyclohexyl- 2-en-1-one (Compound No. 119);
2- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) benzoyl-2-methyl-4-nitro) -3-hydroxy Cyclohex-2-en-1-one (Compound No. 120);
2- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-methyl-4-nitro-benzoyl) -3-oxo-bicyclo 1-yl-acetate (Compound No. 121);
2- (3- (2- (2- (H 2 -1,2,3- triazine-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Hydroxycyclohex-2-en-1-one (Compound No. 123);
2- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Oxocyclohexyl-1-en-1-yl acetate (Compound No. 124);
2- (3- (2- (2- ( 2 H -1,2,3- triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Cyclohex-2-en-1-one (Compound No. 125);
(3-chloro-2- (3- (2-fluoro-2- (1 H -1,2,3- triazol- 1 -yl) Cyclohex-2-en-1-one (Compound No. 133);
3-chloro-2- (3- (2-methyl-4- (methylsulfonyl) to 2- (2 H -1,2,3- triazol-2-yl) 2-fluoro-benzoyl) Cyclohex-2-en-1-one (Compound No. 135);
2- (3- (2-methyl-4- (methylsulfonyl) on -2- (2 H -1,2,3- triazol-2-yl) 2-fluoro-benzoyl) -3-oxo Cyclohex-1-en-1-yl acetate (Compound No. 136); And
Lt; RTI ID = 0.0 > pharmaceutically < / RTI > acceptable salts thereof.
하기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 1종 이상의 활성성분 0.1 중량% 내지 99.9 중량%; 및
계면활성제와 고체 또는 액체 희석제로 이루어진 군으로부터 선택된 1종 이상의 첨가제 0.1 중량% 내지 99.9 중량%; 를 포함하는 제초제 조성물.
[화학식 1]
Figure pat00054

(상기 화학식 1에서, R1, R2, R3, R4, X, Y, Z 및 n은 각각 상기 청구항 1에서 정의한 바와 같다)
0.1 to 99.9% by weight of at least one active ingredient selected from the group consisting of benzoylcyclohexanedione compounds represented by the following formula (1) and pesticidally acceptable salts thereof; And
0.1% to 99.9% by weight of at least one additive selected from the group consisting of surfactants and solid or liquid diluents; ≪ / RTI >
[Chemical Formula 1]
Figure pat00054

Wherein R 1 , R 2 , R 3 , R 4 , X, Y, Z and n are the same as defined in claim 1,
제 6 항에 있어서,
상기 조성물이 수화제, 현탁제, 유제, 유탁제, 미탁제, 액제, 분산성 액제, 입상수화제, 입제, 분제, 액상수화제, 입상수화제, 수면부상성입제, 또는 정제로 제제화된 것을 특징으로 하는 제초제 조성물.
The method according to claim 6,
Characterized in that the composition is formulated with a wetting agent, a suspending agent, an emulsion, an emulsion, a mist, a liquid, a dispersing liquid, a granular wetting agent, a granule, a powder, a liquid wettable powder, a granular wettable powder, .
제 6 항에 있어서,
상기 활성성분은 추가로 아세틸-CoA 카르복실라제 억제제(ACC), 아세토락테이트 신타제 억제제(ALS), 아미드, 옥신 제초제, 옥신 수송 억제제, 카로테노이드 생합성 억제제, 에놀피루빌시키메이트 3-포스페이트 신타제 억제제(ESPS), 글루타민 신테타제 억제제, 지질 생합성 억제제, 유사분열 억제제, 프로토포르피리노겐 IX 옥시다제 억제제, 광합성 억제제, 상승작용제, 성장 물질, 세포벽 생합성 억제제, 및 공지 제초제로 이루어지는 군으로부터 선택되는 하나 또는 그 이상의 성분을 더 포함하는 것을 특징으로 하는 제초제 조성물.
The method according to claim 6,
The active ingredient may further comprise at least one of an acetyl-CoA carboxylase inhibitor (ACC), a acetolactate synthase inhibitor (ALS), an amide, an auxin herbicide, an auxin transport inhibitor, a carotenoid biosynthesis inhibitor, Or a herbicide selected from the group consisting of a plant growth regulator, an inhibitor of growth factor (ESPS), a glutamine synthetase inhibitor, a lipid biosynthesis inhibitor, a mitotic inhibitor, a protoporphyrinogen IX oxidase inhibitor, a photosynthesis inhibitor, 0.0 > and / or < / RTI > further components.
제 6 항 내지 제 8 항으로 이루어진 군으로부터 선택된 제초제 조성물을 처리하여 잡초를 방제하는 방법.
A method for controlling weeds by treating a herbicidal composition selected from the group consisting of the claims 6 to 8.
제 9항에 있어서, 수면처리 또는 경엽처리하여 잡초를 방제하는 방법.
The method according to claim 9, wherein the weeds are treated by water treatment or foliar treatment.
제 9 항에 있어서,
벼에는 안전하면서, 화본과 잡초, 사초과 잡초, 광엽 잡초, 또는 이들의 조합을 방제하는 방법.
10. The method of claim 9,
A method for controlling crops, weeds, shoots and weeds, light weeds, or combinations thereof, while being safe for rice.
제 9 항에 있어서,
바랭이, 수수, 돌피, 올챙이고랭이, 물달개비, 까마중 또는 도꼬마리로 이루어진 군으로부터 선택된 잡초를 방제하는 방법.
10. The method of claim 9,
A method for controlling weeds, which is selected from the group consisting of barren, sorghum, molasses, tadpole, lobster,
하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시 벤조에이트와 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약을 반응시켜 제조하는, 하기 화학식 1a로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법 :
Figure pat00055

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 청구항 1에서 정의한 바와 같다)
A process for producing benzoyl cyclohexanedione represented by the following formula (1a), which is prepared by reacting 3-oxo-1-cycloalkenyl-3-alkoxybenzoate represented by the following formula (2) with acetone cyanohydrin reagent represented by the following formula Preparation of the compound:
Figure pat00055

(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in claim 1, respectively)
제 13 항에 있어서,
상기 반응은 시안화 화합물과 염기 존재 하에서 수행하는 것을 특징으로 하는 벤조일사이클로헥사다이온 화합물의 제조방법.
14. The method of claim 13,
Wherein the reaction is carried out in the presence of a cyanide compound and a base.
하기 화학식 1a로 표시되는 화합물을 할로젠화 시약과 반응시켜 제조하는, 하기 화학식 1b로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법 :
Figure pat00056

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 청구항 1에서 정의한 바와 같고, Hal.은 할로젠원자를 나타낸다)
A process for producing a benzoylcyclohexanedione compound represented by the following formula (1b), which is prepared by reacting a compound represented by the following formula (1a) with a halogenating reagent:
Figure pat00056

(Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in claim 1, and Hal. Represents a halogen atom)
하기 화학식 1a로 표시되는 화합물을 R6-C(O)-Cl로 표시되는 알킬카르보닐 클로라이드와 반응시켜 제조하는, 하기 화학식 1c로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법 :
Figure pat00057

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 청구항 1에서 정의한 바와 같고, R6는 C1∼C4알킬기를 나타낸다.)
A process for producing a benzoylcyclohexanedione compound represented by the following formula (1c), which comprises reacting a compound represented by the formula (1a) with an alkylcarbonyl chloride represented by R 6 -C (O)
Figure pat00057

Wherein R 2 , R 3 , R 4 , X, Y, Z and n are as defined in claim 1 and R 6 represents a C 1 -C 4 alkyl group.
제 13 항에 있어서,
상기 화학식 2로 표시되는 화합물은 하기 4단계의 과정을 수행하여 제조된 것을 특징으로 하는 벤조일사이클로헥사다이온 화합물의 제조방법 :
ⅰ단계) 하기 화학식 5로 표시되는 치환된 메틸 하이드록시벤조에이트를 다이브로모알칸 시약과 반응시켜, 하기 화학식 6으로 표시되는 치환된 메틸 브로모알콕시 벤조에이트를 제조하는 과정;
Figure pat00058

(상기 반응식에서, R4, X 및 Y는 각각 상기 청구항 1에서 정의한 바와 같다)
ⅱ단계) 하기 화학식 6으로 표시되는 화합물을 Z-H로 표시되는 아졸시약과 반응시켜, 하기 화학식 7로 표시되는 화합물을 제조하는 과정;
Figure pat00059

(상기 반응식에서, R4, X, Y 및 Z는 각각 상기 청구항 1에서 정의한 바와 같다)
ⅲ단계) 하기 화학식 7로 표시되는 화합물을 가수분해 반응시켜, 하기 화학식 8로 표시되는 벤조산 화합물을 제조하는 과정; 및
Figure pat00060

(상기 반응식에서, R4, X, Y 및 Z는 각각 상기 청구항 1에서 정의한 바와 같다)
ⅳ단계) 하기 화학식 6으로 표시되는 화합물을 하기 화학식 7로 표시되는 사이클로알칸 다이온 시약과 반응시켜, 하기 화학식 2로 표시되는 화합물을 제조하는 과정.
Figure pat00061

(상기 반응식에서, R4, X, Y 및 Z는 각각 상기 청구항 1에서 정의한 바와 같다)
14. The method of claim 13,
Wherein the compound represented by Formula 2 is prepared by performing the following four steps:
(I) preparing a substituted methyl bromoalkoxybenzoate represented by the following formula (6) by reacting a substituted methylhydroxybenzoate represented by the following formula (5) with a dibromoalkane reagent;
Figure pat00058

(Wherein R 4 , X and Y are as defined in claim 1, respectively)
(Ii) a step of reacting a compound represented by the following formula (6) with an azole reagent represented by ZH to prepare a compound represented by the following formula (7);
Figure pat00059

(Wherein R 4 , X, Y and Z are the same as defined in claim 1, respectively)
(Iii) a step of hydrolyzing a compound represented by the formula (7) to prepare a benzoic acid compound represented by the following formula (8); And
Figure pat00060

(Wherein R 4 , X, Y and Z are the same as defined in claim 1, respectively)
(Iv) a step of reacting a compound represented by the following formula (6) with a cycloalkanedione reagent represented by the following formula (7) to prepare a compound represented by the following formula (2).
Figure pat00061

(Wherein R 4 , X, Y and Z are the same as defined in claim 1, respectively)
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003066607A1 (en) 2002-02-08 2003-08-14 Bayer Cropscience Aktiengesellschaft Novel tetrazole derivative useful as herbicides
KR20100034734A (en) * 2007-08-01 2010-04-01 구미아이 가가쿠 고교 가부시키가이샤 Oxopyrazine derivative and herbicide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003066607A1 (en) 2002-02-08 2003-08-14 Bayer Cropscience Aktiengesellschaft Novel tetrazole derivative useful as herbicides
KR20040081193A (en) * 2002-02-08 2004-09-20 바이엘 크롭사이언스 아게 Novel tetrazole derivative useful as herbicides
KR20100034734A (en) * 2007-08-01 2010-04-01 구미아이 가가쿠 고교 가부시키가이샤 Oxopyrazine derivative and herbicide

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