JPH0580476B2 - - Google Patents
Info
- Publication number
- JPH0580476B2 JPH0580476B2 JP26970986A JP26970986A JPH0580476B2 JP H0580476 B2 JPH0580476 B2 JP H0580476B2 JP 26970986 A JP26970986 A JP 26970986A JP 26970986 A JP26970986 A JP 26970986A JP H0580476 B2 JPH0580476 B2 JP H0580476B2
- Authority
- JP
- Japan
- Prior art keywords
- nornicotine
- och
- compound
- formula
- hereinafter referred
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- MYKUKUCHPMASKF-VIFPVBQESA-N (S)-nornicotine Chemical class C1CCN[C@@H]1C1=CC=CN=C1 MYKUKUCHPMASKF-VIFPVBQESA-N 0.000 claims description 30
- MYKUKUCHPMASKF-UHFFFAOYSA-N Nornicotine Natural products C1CCNC1C1=CC=CN=C1 MYKUKUCHPMASKF-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000035784 germination Effects 0.000 claims description 14
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 8
- 101150065749 Churc1 gene Proteins 0.000 claims description 8
- 102100038239 Protein Churchill Human genes 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000002401 inhibitory effect Effects 0.000 description 10
- -1 5-hydroxypentanoyl Chemical group 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 3
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 3
- 241000208128 Nicotiana glauca Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- OJRUSAPKCPIVBY-KQYNXXCUSA-N C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N Chemical compound C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N OJRUSAPKCPIVBY-KQYNXXCUSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000219295 Portulaca Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003855 acyl compounds Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
〔産業上の利用分野〕
本発明は新規かつ有用なノルニコチン誘導体と
その製造法及びその用途に関する。これらの化合
物は発芽阻害作用を有し、発芽阻害剤として有用
である。
〔従来の技術〕
従来、発芽阻害作用を有する化合物は除草剤な
どとして多数知られている（例えば特開昭61−
69778号公報）。また、本発明者は先に野生種のた
ばこ植物中に発芽阻害作用を有する新規なノルニ
コチン誘導体が含まれていることを見出し、これ
を抽出精製して化学構造を決定し特許出願を行つ
た（出願中）。
〔発明が解決しようとする問題点〕
前記発芽阻害作用を有する新規ノルニコチン誘
導体は野生種たばこに含まれる天然成分であり、
これを農薬として利用する場合には、該植物を栽
培し、成分を抽出しなければならず、コストが高
くなる欠点がある。
〔問題点を解決するための手段〕
本発明者は、前記した野生種たばこ植物中に含
有される新規ノルニコチン誘導体が植物種子に対
して発芽阻害作用を有するという発見に基づき、
類似のノルニコチン誘導体を数多く化学合成して
発芽阻害活性を調べたところ、ノルニコチンのア
シル化合物中に天然物と同等ないしそれを上回る
作用があることを認め本発明をなすに至つた。
すなわち、本発明は次式に示すノルニコチン誘
導体とその製造法及び該化合物を有効成分として
含有する発芽阻害剤である。
[Industrial Application Field] The present invention relates to a new and useful nornicotine derivative, its production method, and its use. These compounds have a germination inhibitory effect and are useful as germination inhibitors. [Prior Art] Conventionally, many compounds having a germination inhibiting effect have been known as herbicides (for example, Japanese Patent Application Laid-Open No. 1983-1999).
Publication No. 69778). In addition, the present inventor previously discovered that wild tobacco plants contain a novel nornicotine derivative that has a germination-inhibiting effect, extracted and purified it, determined its chemical structure, and filed a patent application ( (pending). [Problems to be solved by the invention] The novel nornicotine derivative having a germination inhibiting effect is a natural component contained in wild tobacco,
When using this as a pesticide, the plant must be cultivated and the components must be extracted, which has the drawback of increasing costs. [Means for solving the problem] Based on the discovery that the novel nornicotine derivative contained in the above-mentioned wild tobacco plants has a germination inhibiting effect on plant seeds,
After chemically synthesizing a number of similar nornicotine derivatives and examining their germination-inhibiting activity, the inventors found that the acyl compound of nornicotine has an effect equal to or superior to that of natural products, leading to the present invention. That is, the present invention is a nornicotine derivative represented by the following formula, a method for producing the same, and a germination inhibitor containing the compound as an active ingredient.
【式】
上記一般式中、Ｒは次の(1)〜(18)を表す。
(1) Ｃ＝Ｏ（CH2）8CH3，
(2) Ｃ＝Ｏ（CH2）10CH3，
(3) Ｃ＝Ｏ（CH2）12CH3，
(4) Ｃ＝Ｏ（CH2）14CH3，
(5) Ｃ＝Ｏ（CH2）7（CH＝CHCH2）2（CH2）3
CH3，
(6) Ｃ＝Ｏ（CH2）7（CH＝CHCH2）3CH3，
(7) Ｃ＝OCH2CH2Ｃ＝OCH3，
(8) Ｃ＝OCH2CH（OH）CH3，
(9) Ｃ＝Ｏ（CH2）2CH2（OH），
(10) Ｃ＝Ｏ（CH2）3CH2（OH），
(11) Ｃ＝Ｏ（CH2）2CH（OH）CH3，
(12) Ｃ＝Ｏ（CH2）4CH2（OH），
(13) Ｃ＝Ｏ（CH2）2CH（OH）（CH2）4CH3，
(14) Ｃ＝Ｏ（CH2）3CH（OH）（CH2）3CH3，
(15) Ｃ＝Ｏ（CH2）3CH（OH）（CH2）4CH3，
(16) Ｃ＝Ｏ（CH2）2CH（OH）（CH2）6CH3，
(17) Ｃ＝Ｏ（CH2）2CH（OH）（CH2）7CH3，
(18) Ｃ＝Ｏ（CH2）3CH（OH）（CH2）6CH3，
上記一般式で示される化合物は、それぞれN1
−デカノイルノルニコチン（以下、化合物１と記
載する）、N1−ドデカノイルノルニコチン（以
下、化合物２と記載する）、N1−テトラデカノイ
ルノルニコチン（以下、化合物３と記載する）、
N1−ヘキサデカノイルノルニコチン（以下、化
合物４と記載する）、N1−リノレニルノルニコチ
ン（以下、化合物５と記載する）、N1−リノレイ
ルノルニコチン（以下、化合物６と記載する）、
N1−レブリニルノルニコチン（以下、化合物７
と記載する）、N1−（３−ヒドロキシブタノイル）
ノルニコチン（以下、化合物８と記載する）、N1
−（４−ヒドロキシブタノイル）ノルニコチン
（以下、化合物９と記載する）、N1−（５−ヒドロ
キシペンタノイル）ノルニコチン（以下、化合物
10と記載する）、N1−（４−ヒドロキシペンタノ
イル）ノルニコチン（以下、化合物11と記載す
る）、N1−（６−ヒドロキシヘキサノイル）ノル
ニコチン（以下、化合物12と記載する）、N1−
（４−ヒドロキシノナノイル）ノルニコチン（以
下、化合物13と記載する）、N1−（５−ヒドロキ
シノナノイル）ノルニコチン（以下、化合物14と
記載する）、N1−（５−ヒドロキシデカノイル）
ノルニコチン（以下、化合物15と記載する）、N1
−（５−ヒドロキシウンデカノイル）ノルニコチ
ン（以下、化合物16と記載する）、N1−（４−ヒ
ドロキシドデカノイル）ノルニコチン（以下、化
合物17と記載する）、N1−（５−ヒドロキシドデ
カノイル）ノルニコチン（以下、化合物18と記載
する）である。
次に、化合物１から18についての物性値として
質量分析計によるマススペクトルを表−１に示
す。
これらノルニコチン誘導体（以下、本化合物と
もいう）は触媒として含水酸化ジルコニウムを用
い、カルボン酸、オキソカルボン酸、またはラク[Formula] In the above general formula, R represents the following (1) to (18). (1) C=O(CH 2 ) 8 CH 3 , (2) C=O(CH 2 ) 10 CH 3 , (3) C=O(CH 2 ) 12 CH 3 , (4) C=O(CH 2 ) 14 CH 3 , (5) C=O(CH 2 ) 7 (CH=CHCH 2 ) 2 (CH 2 ) 3
CH 3 , (6) C=O(CH 2 ) 7 (CH=CHCH 2 ) 3 CH 3 , (7) C=OCH 2 CH 2 C=OCH 3 , (8) C=OCH 2 CH(OH)CH 3 , (9) C=O(CH 2 ) 2 CH 2 (OH), (10) C=O(CH 2 ) 3 CH 2 (OH), (11) C=O(CH 2 ) 2 CH(OH )CH 3 , (12) C=O(CH 2 ) 4 CH 2 (OH), (13) C=O(CH 2 ) 2 CH(OH)(CH 2 ) 4 CH 3 , (14) C=O (CH 2 ) 3 CH (OH) (CH 2 ) 3 CH 3 , (15) C=O (CH 2 ) 3 CH (OH) (CH 2 ) 4 CH 3 , (16) C=O (CH 2 ) 2 CH(OH)(CH 2 ) 6 CH 3 , (17) C=O(CH 2 ) 2 CH(OH)(CH 2 ) 7 CH 3 , (18) C=O(CH 2 ) 3 CH(OH )(CH 2 ) 6 CH 3 , the compounds represented by the above general formula are each N 1
-decanoylnornicotine (hereinafter referred to as compound 1), N1 -dodecanoylnornicotine (hereinafter referred to as compound 2), N1 -tetradecanoylnornicotine (hereinafter referred to as compound 3),
N 1 -hexadecanoylnornicotine (hereinafter referred to as compound 4), N 1 -linolenylnornicotine (hereinafter referred to as compound 5), N 1 -linoleylnornicotine (hereinafter referred to as compound 6) ),
N 1 -levulinylnornicotine (hereinafter, compound 7
), N 1 -(3-hydroxybutanoyl)
Nornicotine (hereinafter referred to as compound 8), N 1
-(4-hydroxybutanoyl)nornicotine (hereinafter referred to as compound 9), N1- (5-hydroxypentanoyl)nornicotine (hereinafter referred to as compound 9),
10), N1- (4-hydroxypentanoyl)nornicotine (hereinafter referred to as compound 11), N1- (6-hydroxyhexanoyl)nornicotine (hereinafter referred to as compound 12), N1 −
(4-hydroxynonanoyl)nornicotine (hereinafter referred to as compound 13), N1- (5-hydroxynonanoyl)nornicotine (hereinafter referred to as compound 14), N1- (5-hydroxydecanoyl)
Nornicotine (hereinafter referred to as compound 15), N 1
-(5-hydroxyundecanoyl)nornicotine (hereinafter referred to as compound 16), N1- (4-hydroxydodecanoyl)nornicotine (hereinafter referred to as compound 17), N1- (5-hydroxydodecanoyl) ) nornicotine (hereinafter referred to as compound 18). Next, Table 1 shows mass spectra measured by a mass spectrometer as physical property values for Compounds 1 to 18. These nornicotine derivatives (hereinafter also referred to as the present compounds) use hydrous zirconium oxide as a catalyst to produce carboxylic acids, oxocarboxylic acids, or lacquer.
ノルニコチン740mg（5mmol）、内標としてヘ
キサデカン0.5mmol、キシレン10ｇ、含水酸化ジ
ルコニウム2.5ｇを４つの100mlナスフラスコにそ
れぞれ入れ、デカン酸をそれぞれに50mmol，
25mmol，10mmol，5mmol加えた。各フラスコ
に還流管を付し、マントルヒーター中で加熱還流
した。７時間後のノルニコチン誘導体の収率を表
−３に示す。
表−３
ノルニコチン：デカン酸 収率（％）
１：10 98
１：５ 89
１：２ 95
１：１ 75
以上よりノルニコチンに対してデカン酸は２倍
当量以上使用することが望ましい。
〔実施例 ３〕
ノルニコチン20mmolとラクトン200mlをトル
エンに溶解させ含水酸化ジルコニウム５ｇを加え
て２時間加熱還流させた。反応液を冷却後ろ過に
より含水酸化ジルコニウムを除去しジエチルエー
テル50ml加えた。10％炭酸カリウム水溶液50mlを
使つて洗浄後エーテル層を無水硫酸ナトリウムで
脱水した。ロータリーエバホペレーターを用いジ
エチルエーテルを留去し残査をシリカゲルカラム
に吸着させた。エーテル200ml、メタノール：エ
ーテル（５：95）200ml、メタノール：エーテル
（10：90）300ml、メタノール：エーテル（20：
80）300mlで順次展開し100mlずつ分取した。各フ
ラクシヨンをガスクロマトグラフを使つて分析し
たところ、メタノール：エーテル（20：80）300
mlの分画にアシル化されたノルニコチンの流出が
認められた。この生成物の含まれているフシラク
シヨンをあつめロータリーエバポレーターで溶媒
を除去しガスクロマトグラフにより純度を求めて
表−４の結果を得た。
表−４
化合物番号 収率（％） 純度（％）
８ 98.8 94
９ 85.4 98
10 98.7 98
11 74.0 99
12 96.8 99
13 60.5 99.7
14 97.2 95
15 98.1 99
16 67.1 99
17 62.1 99
18 97.7 99
〔実施例 ４〕
得られたノルニコチン誘導体の発芽阻害活性は
次のようにして調べた。直径25mmの秤量菅に一定
量の被検物質を加えた水溶液により浸積したろ紙
を置き、発芽阻害を見るための種々を一定量播種
する。播種後、25℃、12時間明暗の恒温室に静置
し、発芽成長の度合いから阻害活性を判定した。
なお判定は次の基準によつた。
生長阻害指数は４：完全阻害、３：75％阻害、
２：50％阻害、１：25％阻害、０：効力なしを表
す。対照には、水のみを用いた。結果を表−５に
示した。
Put 740 mg (5 mmol) of nornicotine, 0.5 mmol of hexadecane as an internal standard, 10 g of xylene, and 2.5 g of hydrous zirconium oxide into four 100 ml eggplant flasks, and add 50 mmol of decanoic acid to each.
Added 25mmol, 10mmol, and 5mmol. Each flask was equipped with a reflux tube and heated to reflux in a mantle heater. Table 3 shows the yield of nornicotine derivative after 7 hours. Table 3 Nornicotine: Decanoic acid Yield (%) 1:10 98 1:5 89 1:2 95 1:1 75 From the above, it is desirable to use at least twice the equivalent amount of decanoic acid relative to nornicotine. [Example 3] 20 mmol of nornicotine and 200 ml of lactone were dissolved in toluene, 5 g of hydrous zirconium oxide was added, and the mixture was heated under reflux for 2 hours. After cooling the reaction solution, hydrous zirconium oxide was removed by filtration, and 50 ml of diethyl ether was added. After washing with 50 ml of 10% potassium carbonate aqueous solution, the ether layer was dehydrated with anhydrous sodium sulfate. Diethyl ether was distilled off using a rotary evaporator, and the residue was adsorbed onto a silica gel column. 200ml of ether, 200ml of methanol:ether (5:95), 300ml of methanol:ether (10:90), 300ml of methanol:ether (20:
80) Developed sequentially with 300 ml and collected 100 ml each. When each fraction was analyzed using a gas chromatograph, methanol:ether (20:80) 300
Outflow of acylated nornicotine was observed in the ml fraction. The fusilaxion containing this product was collected, the solvent was removed using a rotary evaporator, and the purity was determined using gas chromatography to obtain the results shown in Table 4. Table-4 Compound number Yield (%) Purity (%) 8 98.8 94 9 85.4 98 10 98.7 98 11 74.0 99 12 96.8 99 13 60.5 99.7 14 97.2 95 15 98.1 99 16 67.1 99 17 62 .1 99 18 97.7 99 [Example 4] The germination inhibitory activity of the obtained nornicotine derivative was examined as follows. A filter paper soaked with an aqueous solution containing a certain amount of the test substance is placed in a weighing tube with a diameter of 25 mm, and a certain amount of various seeds are sown to check for germination inhibition. After sowing, the seeds were placed in a constant temperature room at 25°C with light and darkness for 12 hours, and the inhibitory activity was determined from the degree of germination and growth.
The judgment was based on the following criteria. Growth inhibition index is 4: complete inhibition, 3: 75% inhibition,
2: 50% inhibition, 1: 25% inhibition, 0: no efficacy. Water alone was used as a control. The results are shown in Table-5.
実施例４に従つて一連のノルニコチン誘導体の
スベリヒユ種子に対する生育阻害活性を検討し
た。
結果を表−６に示した。
According to Example 4, the growth inhibitory activity of a series of nornicotine derivatives on Portulaca seeds was investigated. The results are shown in Table-6.
【表】【table】
実施例から本発明のノルニコチン誘導体が発芽
阻害効果をもつことは明らかであり、本発明によ
り新規な発芽阻害剤を提供する。
It is clear from the examples that the nornicotine derivative of the present invention has a germination inhibitory effect, and the present invention provides a novel germination inhibitor.
Claims (1)
酸、またはラクトンをノルニコチンに反応させる
ことにより、ノルニコチン誘導体を合成する方法
において、触媒として含水酸化ジルコニウムを用
いることを特徴とする一般式（）で示されるノ
ルニコチン誘導体の合成法。 【式】 （式 （）中Ｒは、 Ｃ＝Ｏ（CH2）8CH3， Ｃ＝Ｏ（CH2）10CH3， Ｃ＝Ｏ（CH2）12CH3， Ｃ＝Ｏ（CH2）14CH3， Ｃ＝Ｏ（CH2）7（CH＝CHCH2）2（CH2）3CH3， Ｃ＝Ｏ（CH2）7（CH＝CHCH2）3CH3， Ｃ＝OCH2CH2Ｃ＝OCH3， Ｃ＝OCH2CH（OH）CH3， Ｃ＝Ｏ（CH2）2CH2（OH）， Ｃ＝Ｏ（CH2）3CH2（OH）， Ｃ＝Ｏ（CH2）2CH（OH）CH3， Ｃ＝Ｏ（CH2）4CH2（OH）， Ｃ＝Ｏ（CH2）2CH（OH）（CH2）4CH3， Ｃ＝Ｏ（CH2）3CH（OH）（CH2）3CH3， Ｃ＝Ｏ（CH2）3CH（OH）（CH2）4CH3， Ｃ＝Ｏ（CH2）2CH（OH）（CH2）6CH3， Ｃ＝Ｏ（CH2）2CH（OH）（CH2）7CH3， Ｃ＝Ｏ（CH2）3CH（OH）（CH2）6CH3， を表す。） ３ 一般式（） 【式】 で表される化合物を有効成分として含む発芽阻害
剤。 （式 （）中Ｒは、 Ｃ＝Ｏ（CH2）8CH3， Ｃ＝Ｏ（CH2）10CH3， Ｃ＝Ｏ（CH2）12CH3， Ｃ＝Ｏ（CH2）14CH3， Ｃ＝Ｏ（CH2）7（CH＝CHCH2）2（CH2）3CH3， Ｃ＝Ｏ（CH2）7（CH＝CHCH2）3CH3， Ｃ＝OCH2CH2Ｃ＝OCH3， Ｃ＝OCH2CH（OH）CH3， Ｃ＝Ｏ（CH2）2CH2（OH）， Ｃ＝Ｏ（CH2）3CH2（OH）， Ｃ＝Ｏ（CH2）2CH（OH）CH3， Ｃ＝Ｏ（CH2）4CH2（OH）， Ｃ＝Ｏ（CH2）2CH（OH）（CH2）4CH3， Ｃ＝Ｏ（CH2）3CH（OH）（CH2）3CH3， Ｃ＝Ｏ（CH2）3CH（OH）（CH2）4CH3， Ｃ＝Ｏ（CH2）2CH（OH）（CH2）6CH3， Ｃ＝Ｏ（CH2）2CH（OH）（CH2）7CH3， Ｃ＝Ｏ（CH2）3CH（OH）（CH2）6CH3， を表す。）[Claims] 1. A compound represented by the general formula () [Formula]. (Formula, R in () is C=O(CH 2 ) 8 CH 3 , C=O(CH 2 ) 10 CH 3 , C=O(CH 2 ) 12 CH 3 , C=O(CH 2 ) 14 CH 3 , C=O(CH 2 ) 7 (CH=CHCH 2 ) 2 (CH 2 ) 3 CH 3 , C=O(CH 2 ) 7 (CH=CHCH 2 ) 3 CH 3 , C=OCH 2 CH 2 C=OCH 3 , C=OCH 2 CH(OH)CH 3 , C=O(CH 2 ) 2 CH 2 (OH), C=O(CH 2 ) 3 CH 2 (OH), C=O(CH 2 ) 2 CH(OH)CH 3 , C=O(CH 2 ) 4 CH 2 (OH), C=O(CH 2 ) 2 CH(OH)(CH 2 ) 4 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 3 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 4 CH 3 , C=O(CH 2 ) 2 CH(OH)(CH 2 ) 6 Represents CH 3 , C=O(CH 2 ) 2 CH(OH)(CH 2 ) 7 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 6 CH 3 , ) 2 of the catalyst A method for synthesizing nornicotine derivatives by reacting carboxylic acid, oxocarboxylic acid, or lactone with nornicotine in the presence of Synthesis method. [Formula] (R in formula () is C=O(CH 2 ) 8 CH 3 , C=O(CH 2 ) 10 CH 3 , C=O(CH 2 ) 12 CH 3 , C=O(CH 2 ) 14 CH 3 , C=O(CH 2 ) 7 (CH=CHCH 2 ) 2 (CH 2 ) 3 CH 3 , C=O(CH 2 ) 7 (CH=CHCH 2 ) 3 CH 3 , C=OCH 2 CH 2 C=OCH 3 , C=OCH 2 CH(OH)CH 3 , C=O(CH 2 ) 2 CH 2 (OH), C=O(CH 2 ) 3 CH 2 (OH), C=O( CH 2 ) 2 CH(OH)CH 3 , C=O(CH 2 ) 4 CH 2 (OH), C=O(CH 2 ) 2 CH(OH)(CH 2 ) 4 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 3 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 4 CH 3 , C=O(CH 2 ) 2 CH(OH)(CH 2 ) 6 CH 3 , C=O(CH 2 ) 2 CH(OH)(CH 2 ) 7 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 6 CH 3 , represents.) 3 A germination inhibitor containing a compound represented by the general formula () [Formula] as an active ingredient. (R in formula () is C=O(CH 2 ) 8 CH 3 , C=O(CH 2 ) 10 CH 3 , C=O(CH 2 ) 12 CH 3 , C=O(CH 2 ) 14 CH 3 , C=O(CH 2 ) 7 (CH=CHCH 2 ) 2 (CH 2 ) 3 CH 3 , C=O(CH 2 ) 7 (CH=CHCH 2 ) 3 CH 3 , C=OCH 2 CH 2 C =OCH 3 , C=OCH 2 CH(OH)CH 3 , C=O(CH 2 ) 2 CH 2 (OH), C=O(CH 2 ) 3 CH 2 (OH), C=O(CH 2 ) 2 CH(OH)CH 3 , C=O(CH 2 ) 4 CH 2 (OH), C=O(CH 2 ) 2 CH(OH)(CH 2 ) 4 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 3 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 4 CH 3 , C=O(CH 2 ) 2 CH(OH)(CH 2 ) 6 CH 3 , C=O(CH 2 ) 2 CH(OH)(CH 2 ) 7 CH 3 , C=O(CH 2 ) 3 CH(OH)(CH 2 ) 6 CH 3 , represents.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26970986A JPS63126876A (en) | 1986-11-14 | 1986-11-14 | Nornicotine derivative, production thereof and germination inhibitor containing said compound as active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26970986A JPS63126876A (en) | 1986-11-14 | 1986-11-14 | Nornicotine derivative, production thereof and germination inhibitor containing said compound as active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63126876A JPS63126876A (en) | 1988-05-30 |
| JPH0580476B2 true JPH0580476B2 (en) | 1993-11-09 |
Family
ID=17476083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26970986A Granted JPS63126876A (en) | 1986-11-14 | 1986-11-14 | Nornicotine derivative, production thereof and germination inhibitor containing said compound as active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63126876A (en) |
-
1986
- 1986-11-14 JP JP26970986A patent/JPS63126876A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63126876A (en) | 1988-05-30 |
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