JPH0419839B2 - - Google Patents
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- Publication number
- JPH0419839B2 JPH0419839B2 JP59078706A JP7870684A JPH0419839B2 JP H0419839 B2 JPH0419839 B2 JP H0419839B2 JP 59078706 A JP59078706 A JP 59078706A JP 7870684 A JP7870684 A JP 7870684A JP H0419839 B2 JPH0419839 B2 JP H0419839B2
- Authority
- JP
- Japan
- Prior art keywords
- substance
- ampb
- general formula
- group
- eluted
- 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
- 239000000126 substance Substances 0.000 claims description 79
- 150000001875 compounds Chemical class 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 6
- 238000012258 culturing Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 244000005700 microbiome Species 0.000 claims description 3
- 241000187747 Streptomyces Species 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000843 powder Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 235000001014 amino acid Nutrition 0.000 description 19
- 150000001413 amino acids Chemical class 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 235000004279 alanine Nutrition 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 17
- 230000014759 maintenance of location Effects 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 16
- 238000004809 thin layer chromatography Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000002363 herbicidal effect Effects 0.000 description 9
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004009 herbicide Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- FEMOMIGRRWSMCU-UHFFFAOYSA-N ninhydrin Chemical compound C1=CC=C2C(=O)C(O)(O)C(=O)C2=C1 FEMOMIGRRWSMCU-UHFFFAOYSA-N 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- QWCKQJZIFLGMSD-UHFFFAOYSA-N 2-Aminobutanoic acid Natural products CCC(N)C(O)=O QWCKQJZIFLGMSD-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- QWCKQJZIFLGMSD-GSVOUGTGSA-N D-alpha-aminobutyric acid Chemical compound CC[C@@H](N)C(O)=O QWCKQJZIFLGMSD-GSVOUGTGSA-N 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 4
- -1 Na salt Chemical class 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 3
- 241000187391 Streptomyces hygroscopicus Species 0.000 description 3
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000012136 culture method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000004474 valine Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 2
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 2
- 235000005476 Digitaria cruciata Nutrition 0.000 description 2
- 235000006830 Digitaria didactyla Nutrition 0.000 description 2
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 2
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 2
- 244000025670 Eleusine indica Species 0.000 description 2
- 235000014716 Eleusine indica Nutrition 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229920005654 Sephadex Polymers 0.000 description 2
- 239000012507 Sephadex™ Substances 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001295 alanines Chemical class 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 101100313763 Arabidopsis thaliana TIM22-2 gene Proteins 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 244000301850 Cupressus sempervirens Species 0.000 description 1
- 241000234653 Cyperus Species 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 238000009629 microbiological culture Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- JOHZPMXAZQZXHR-UHFFFAOYSA-N pipemidic acid Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCNCC1 JOHZPMXAZQZXHR-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Landscapes
- Peptides Or Proteins (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は除草剤として有用である新規な含燐ペ
プチド化合物の製造法に関する。
特公昭51−639号（特許第827768号）公報に記
載のストレプトミセス・ハイグロスコピクス
（Streptomyces hygroscopicus）SF−1293株
（微工研菌寄996号、昭和46年６月以来、微工研に
寄託してあり、また国際寄託に移行してFERM
−BP130号として寄託してあり、また米国ATCC
にもATCC寄託番号21705号として寄託してあり、
これら寄託所から分譲できる状態にある）を培養
することにより次式
で表わされるSF−1293物質が製造できることは
知られており、またSF−1293物質が除草剤とし
て有用であることも知られている（特開昭54−
67026号公報）。
今般、本発明者らは上記のSF−1293株を培養
すると、SF−1293物質と共に一般式（）の含
燐ペプチド化合物群が培養液中に生産されている
ことを発見し、これら化合物を夫々に単難するこ
とに成功し、またこれら化合物が新規物質であつ
て除草剤として有効であることを見出した。
従つて、本発明によると、次の一般式（）
〔式中、R1およびR2は夫々に水素、メチル基、
エチル基、イソプロピル基、またはハイドロキシ
メチル基を示し、R3は−OHまたは基
The present invention relates to a method for producing a novel phosphorus-containing peptide compound useful as a herbicide. Streptomyces hygroscopicus SF-1293 strain described in the Japanese Patent Publication No. 51-639 (Patent No. 827768) (Feikoken Bokuyori No. 996, since June 1970, in the FIKEN) It has been deposited, and it has been transferred to international deposit and FERM
−Deposited as BP130 and also by the US ATCC
It has also been deposited with ATCC deposit number 21705.
By culturing these (available for distribution from these depositories), the following formula is obtained: It is known that the SF-1293 substance represented by can be produced, and it is also known that the SF-1293 substance is useful as a herbicide (Japanese Patent Application Laid-Open No. 1989-1999).
Publication No. 67026). Recently, the present inventors discovered that when the above SF-1293 strain was cultured, a group of phosphorus-containing peptide compounds of the general formula () were produced in the culture solution together with the SF-1293 substance, and these compounds were They succeeded in finding that these compounds are new substances and are effective as herbicides. Therefore, according to the invention, the following general formula () [In the formula, R 1 and R 2 are hydrogen, methyl group,
Represents an ethyl group, isopropyl group, or hydroxymethyl group, and R 3 is -OH or a group
【式】を示し、ただし
R3が基−OHであるときR1とR2が共にメチル基
の場合は除く〕で表わされる、新規な含燐ペプチ
ド化合物が提供される。
一般式（）の含燐ペプチド化合物の塩の例と
しては、この化合物のモノ−、ジ−又はトリ−又
はテトラ−アルカリ金属塩、例えばNa塩、Ｋ
塩；アンモニウム塩；アルカリ土類金属塩、金属
塩があり、また各種の塩基、例えばアルキルアミ
ンとの塩、ならびにコリンとの塩がある。
詳しく言えば、本発明によると、スロレプトミ
セス属に属する次の一般式（）
〔式中、R1およびR2は夫々に水素、メチル基、
エチル基、イソプロピル基またはハイドロキシメ
チル基を示し、R3は基−OHまたは基
Provided is a novel phosphorus-containing peptide compound represented by the formula: except when R 3 is a group -OH and R 1 and R 2 are both methyl groups. Examples of salts of the phosphorus-containing peptide compound of general formula () include mono-, di-, tri- or tetra-alkali metal salts of this compound, such as Na salt, K
Salts; ammonium salts; alkaline earth metal salts, metal salts; and salts with various bases, such as alkylamines, and choline. In particular, according to the present invention, the following general formula () belonging to the genus Throleptomyces [In the formula, R 1 and R 2 are hydrogen, methyl group,
Represents an ethyl group, isopropyl group or hydroxymethyl group, R 3 is a group -OH or a group
【式】を示し、ただし
R3が基−OHであるときR1とR2が共にメチル基
の場合は除く〕で表わされる含燐ペプチド化合物
の生産菌を培養し、この一般式（）の化合物を
培養物から採取することを特徴とする、一般式
（）の含燐ペプチド化合物の製造法が提供され
る。
本発明の方法に使用される一般式（）化合物
生産菌の一例としては、特公昭51−639号公報記
載の、ストレプトミセス・ハイグロスコピクス
SF−1293株（FERM−P996；FERM−BP130）
がある。このSF−1293株の菌学的性質、培養方
法は、特公昭51−639号公報記載の通りである。
一般式（）の化合物はSF−1293株を培養する
場合には特公昭51−639号公報記載のSF−1293物
質（上記一般式（）で、R1＝CH3、R2＝CH3、
R3＝OHの場合）と共に培養液中に生産されるか
ら、SF−1293物質と共に分離し、これからの単
離を含めた精製が必要となる。通常は、SF−
1293株を培養し、その培養ろ液を使い、陽または
陰イオン交換樹脂、薄層クロマトグラフイー、高
速液体クロマトグラフイー、ダイヤイオンHP−
20等の多孔性樹脂によるクロマトグラフイーを組
み合わせることにより、SF−1293物質から単離
して一般式（）の化合物が採取できる。
本発明の方法では本発明化合物生産菌、例えば
SF−1293株を通常の微生物が利用しうる栄養物
を含有する倍地で培養する。栄養源としては、従
来ストレプトミセス属の菌の培養に利用されてい
る公知のものが使用される。例えば炭素源として
グルコース、澱粉、グリセリン、シユクロース、
水あめ、糖密等を使用しうる。また窒素源として
大豆粉、小麦胚芽、肉エキス、ペプトン、乾燥酵
母、コーンステイープリカー、硫酸アンモニウ
ム、硝酸ナトリウム等を使用しうる。その他必要
に応じて炭酸カルシウム、食塩、塩化カリ、燐酸
塩等の無機塩類を添加するほか、菌の発育を助
け、本発明化合物の生産を促進する有機及び無機
物を適当に添加することが出来る。
培養法としては、一般抗生物質生産の方法と同
じく、液体培養法、特に深部培養法が最も適して
いる。SF−1293株を用いる培養は好気的条件下
で行われ、培養に適当な温度は25〜35℃である
が、多くの場合、28℃付近で培養する。かくして
本発明化合物の生産は振盪培養、タンク培養共に
３〜５日で最高に達する。
SF−1293物質及び一般式（）の化合物は主
として培養物の液体部分に存在するが後記の理化
学性状で示すように水溶性の両性物質であるの
で、培養液からの抽出にあたつてはアンバーライ
トIR−120、ダウエツクス50W等の陽イオン交換
樹脂もしくはアンバーライトIRA−400、IR−
45、IR−4B等の陰イオン交換樹脂を使用して吸
着させ、これを適当な酸、アルカリもしくは塩溶
液、を用いて溶出することが出来る。
例えば培養炉液を陽イオン交換樹脂ダウエツク
ス50W（Ｈ型）の樹脂塔を通過させ、有効成分を
樹脂部に吸着させ、これをアンモニア水で溶出す
る方法は有効な抽出手段である。
このような方法で得られたSF−1293物質と一
般式（）の化合物とを含む粗粉末はダウエツク
ス１×２樹脂又はセルロース、シリカゲル、アル
ミナ乃至はセフアデツクスを使用するクロマトグ
ラフイーにかけると、SF−1293物質から一般式
（）の化合物を分離できる。
このように分離された一般式（）の化合物は
更にダウエツクス１×２樹脂を用いるクロマトグ
ラフイーにより、また非イオン性吸着樹脂による
クロマトグラフイー、セルロース薄層クロマトグ
ラフイー及び高速液体クロマトグラフイーを組合
せて目的物質を単離、精製することができる。
一般式（）の化合物の具体例には、下記の物
質がある。
[Formula], except when R 3 is a group -OH and R 1 and R 2 are both methyl groups] is cultured, and this general formula () is Provided is a method for producing a phosphorus-containing peptide compound of general formula (), characterized in that the compound is collected from a culture. An example of a bacterium producing the compound of the general formula () used in the method of the present invention is Streptomyces hygroscopicus described in Japanese Patent Publication No. 51-639.
SF-1293 strain (FERM-P996; FERM-BP130)
There is. The mycological properties and culture method of this SF-1293 strain are as described in Japanese Patent Publication No. 1983-639.
When culturing SF-1293 strain, the compound of general formula () is the SF-1293 substance described in Japanese Patent Publication No. 51-639 (in the above general formula (), R 1 = CH 3 , R 2 = CH 3 ,
Since it is produced in the culture medium together with SF-1293 (in the case of R 3 =OH), it is necessary to separate it together with the SF-1293 substance and purify it, including isolation from it. Usually SF-
1293 strain and using the culture filtrate, cation or anion exchange resin, thin layer chromatography, high performance liquid chromatography, Diaion HP-
By combining chromatography using a porous resin such as 20, the compound of the general formula () can be isolated from the SF-1293 substance. In the method of the present invention, microorganisms producing the compound of the present invention, e.g.
Strain SF-1293 is cultured in a medium containing nutrients that can be used by common microorganisms. As the nutrient source, known nutrient sources conventionally used for culturing Streptomyces bacteria are used. For example, as a carbon source, glucose, starch, glycerin, sucrose,
Starch syrup, molasses, etc. can be used. Also, soybean flour, wheat germ, meat extract, peptone, dry yeast, cornstarch liquor, ammonium sulfate, sodium nitrate, etc. can be used as the nitrogen source. In addition to adding inorganic salts such as calcium carbonate, common salt, potassium chloride, and phosphates as necessary, organic and inorganic substances that aid the growth of bacteria and promote the production of the compound of the present invention may be appropriately added. As for the culture method, the liquid culture method, especially the deep culture method, is most suitable, as is the case with general antibiotic production methods. Cultivation using the SF-1293 strain is performed under aerobic conditions, and the appropriate temperature for cultivation is 25 to 35°C, but in most cases it is cultured at around 28°C. Thus, the production of the compound of the present invention reaches its maximum in 3 to 5 days in both shaking culture and tank culture. The SF-1293 substance and the compound of general formula () mainly exist in the liquid part of the culture, but as shown in the physical and chemical properties below, they are water-soluble amphoteric substances, so when extracting them from the culture solution, amber Cation exchange resins such as Lite IR-120, Dowex 50W, or Amberlite IRA-400, IR-
It can be adsorbed using an anion exchange resin such as 45, IR-4B, and eluted using a suitable acid, alkali or salt solution. For example, an effective extraction method is to pass the culture furnace solution through a resin tower made of cation exchange resin Dowex 50W (H type), to adsorb the active ingredients to the resin part, and to elute this with aqueous ammonia. The coarse powder containing the SF-1293 substance and the compound of general formula () obtained by this method is subjected to chromatography using Dowex 1x2 resin, cellulose, silica gel, alumina, or Cephadex, to obtain SF-1293. −1293 Compounds of general formula () can be separated from substances. The compound of general formula () thus separated was further subjected to chromatography using Dowex 1×2 resin, chromatography using nonionic adsorption resin, cellulose thin layer chromatography, and high performance liquid chromatography. A target substance can be isolated and purified in combination. Specific examples of the compound of general formula () include the following substances.
【表】
これらの化合物は、優れた除草活性をもつこと
が認められた。従つて、一般式（の化合物はこ
れを有効成分として含む除草剤として使用でき、
この除草剤には農薬で常用される担体、補助剤を
配合できる。
また、一般式（）で示される本発明化合物
は、これを加水分解すると、それから次式
で示されるＬ−２−アミノ−４−〔（ヒドロキシ）
（メチル）ホスフイノイル〕酪酸（以下、Ｌ−
AMPBと略称する）を生成することができ、こ
のＬ−AMPBは除草剤として有用である（特開
昭48−85538号、特開昭49−31890号及び特開昭54
−92628号公報参照）。
一般式（）の本発明化合物の生産菌はSF−
1923物質の生産菌である前記のSF−1293株と同
一であるから、SF−1923株の培養液は一般式
（）の本発明化合物とSF−1293株物質とを含有
する。従つて、一般式（）の本発明化合物の生
産菌の培養液からSF−1293物質を分離・精製す
ることなく、その培養液を、公知の加水分解の方
法、例えばアルカリ分解や酸分解、酵素や微生物
培養物を用いた加水分解にかけることによつて、
Ｌ−AMPBを高収率で生成することが可能であ
る。このように、一般式（）の本発明化合物は
除草剤として有効であるＬ−AMPBの製造用原
料としても有用である。
実施例 １
AMPB−Gly−Ala物質（Ia）の製造
(イ) ストレプトミセス・ハイグロスコピクスSF
−1293株（FERM−BP 130）を澱粉2.0％、ペ
プトン1.0％、肉エキス0.3％、リン酸２カリ
0.05％、PH7.0の液体培地15に接種し、28℃
で24時間通気撹拌培養し、これを種母とする。
グルコース3.0％、水あめ1.0％、小麦胚芽2.5
％、ソリユーブル・ベジタブル・プロテイン
0.5％、大豆油0.1％、酵母エキス0.1％、硫酸第
一鉄0.001％、塩化ニツケル0.0001％、塩化コ
バルト0.0001％、PH7.0の液体培地200に前記
種母を接種し、28℃で96時間通気撹拌培養し
た。培養液をPH３で過し、液150を得る
（培養力価110mcg／ml）。
液は活性炭を充填した塔（7.5）を通過
させ、引き続き水30で洗滌する。通過液及び
水洗液を合併し（180）、ダウエツクス50W×
２（50−100メツシユ）（Ｈ型）９の樹脂塔に
かけ有効成分を吸着させる。樹脂塔は水洗後、
0.05Nアンモニア水で溶離する。活性区分（45
）を減圧濃縮し淡黄褐色の粗粉末50ｇ（力価
200mcg／mg）を得た。
(ロ) 上記粗粉末10ｇを水50mlに溶解し、ダウエツ
クス１×２（酢酸型）１を充填したカラムに
通過させて目的物質を吸着させ、２の水でカ
ラムを洗浄した。
次いで0.3規定酢酸６で溶出し、100mlずつ
に分画した。セルロースプレートによる薄層ク
ロマトグラフイー（展開剤：ｎ−ブタノール−
酢酸−水（２：１：１））でRf0.60を示し、高
速液体クロマトグラフイー（ウオーターズ6000
型、カラム：東洋曹達LS410、移動相：0.05M
燐酸緩衝液（PH2.5）、検出：210nｍ）で保持時
間5.9分を示す物質（Ia）を含む分画を集め濃
縮乾固すると、0.85ｇの粉末が得られた。
この粉末を水５mlに溶解し、非イオン性吸着
樹脂ダイヤイオンHP20の400mlを充填したカ
ラムに通過させ、水で展開し10mlづつに分画し
た。セルロースプレートによる薄層クロマトグ
ラフイー及び高速液体クロマトグラフイーで物
質（Ia）のみを含む分画を集め濃縮乾固して物
質（Ia）の白色粉末150mgを得た。
マススペクトル（SIMS）：（Ｍ＋１）+ ｍ／ｚ
310 1H−NMRスペクトル（D2O、pD3）：
δ1.24(d)：AMPBのＰ−CH3、δ1.36(d)：アラニ
ンのCH3、δ1.55〜1.75（ｍ）及びδ1.95〜2.15
（ｍ）：AMPBの２個のCH2、δ3.96（ｑ）：グリ
シンのCH2、δ4.06（ｔ）：AMPBのCH、δ4.29
（ｑ）：アラニンのCH。
本物質（Ia）は、これを６規定塩酸中100℃、
18時間加水分解すると、加水分解物中にAMPB、
グリシン及びアラニンの三種のアミノ酸を検出し
た（アミノ酸分析、薄層クロマトグラフイー）。
また、高速液体クロマトグラフイーの分析で保持
時間5.9分を示した。本物質（Ia）はアミノ酸分
析（アトーKK アミノ酸分析装置MLC−703型、
溶離液PH2.5）で保持時間39分を示した（このと
きSF−1293物質は保持時間35分を示す）。
呈色反応はニンヒドリン、ライドンスミス、ハ
ーネス反応に陽性である。
元素分析値：C38.71、H6.56、N13.38、O31.13
％。
分子式C10H20N3O6Pとしての理論値：C38.83、
H6.52、N13.59、O31.04％。
実施例 ２
AMPB−Ala−Gly物質（Ib）の製造
実施例１(ロ)におけるダウエツクス１×２カラム
の0.3規定酢酸溶出分画のうち、（Ia）物質を含む
分画の前に、高速液体クロマトグラフイーで保持
時間4.5分を示す成分として物質（Ib）の存在が
認められた。物質（Ib）を含む分画を集め濃縮乾
固すると淡褐色粉末3.8ｇが得られた。
この粉末を水10mlに溶解し、ダイヤイオンHP
−20の１を充填し0.02規定塩酸で平衡化したカ
ラムに通過させ更に0.02規定塩酸で展開溶出し
た。
高速液体クロマトグラフイーにより検出し、物
質（Ib）を含む分画を濃縮して約５mlとしたのち
セルロース粉末（フナコシ薬品(株)、アビセル）５
ｇを加え、濃縮乾固した。
別にアビセル粉末をｎ−ブタノール−酢酸−水
−酢酸−ｎブチル（４：１：１：１）で膨潤させ
たもの１を充填したカラムを作製し、これに前
述の物質（Ib）を含むアビセル粉末をのせ、同じ
溶媒で展開溶出した。高速液体クロマトグラフイ
ーでほぼ物質（Ib）のみを含む分画を集め濃縮乾
固すると170mgの白色粉末が得られた。
この粉末を水５mlに溶解し、ダイヤイオンHP
−20の400mlを充填したカラムにかけ水で展開溶
出した。
高速液体クロマトグラフイーで物質（Ib）のみ
を含む分画を集め濃縮乾固し物質（Ib）の白色粉
末45mgを得た。
マススペクトル（SIMS）：（Ｍ＋１）+ ｍ／ｚ
310 1H−NMRスペクトル（D2O、pD1）：
δ1.43(d)：アラニンのCH3、δ1.52(d)：AMPBの
Ｐ−CH3、δ1.8〜2.0（ｍ）及びδ2.05〜2.25
（ｍ）：AMPBの２個のCH2、δ4.0（ｑ）：グリシ
ンのCH2、δ4.10（ｔ）：AMPBのCH、δ4.42
（ｑ）：アラニンのCH。
本物質（Ib）は６規定塩酸中100℃、18時間加
水分解すると、加水分解物中にAMPB、グリシ
ン及びアラニンの三種のアミノ酸を検出した（ア
ミノ酸分析、薄層クロマトグラフイー）。また、
高速液体クロマトグラフイーの分析で保持時間
4.5分を示した。本物質（Ib）はアミノ酸分析で
保持時間40分を示した。
呈色反応はニンヒドリン、ライドンスミス、ハ
ーネス反応に陽性である。
元素分析値：C38.67、H6.48、N13.27、O30.96
％。
分子式C10H20N3O6Pとしての理論値：C38.83、
H6.52、N13.59、O31.04％。
実施例 ３
AMPB−Ala−ABA物質（Ic）の製造
実施例１(イ)で得た粗粉末10ｇに水50mlを加えて
溶解し、ダイヤイオンHP−20 １のカラムに
通過させ水で展開溶出した。SF−1293物質、物
質（Ia）、物質（Ib）等が溶出され終つた後、更
に水て展開溶出すると、薄層クロマトグラフイー
でSF−1293物質（Rf0.65）よりRf値の大きい成
分として物質（Ic）（Rf＝0.77）が溶出されて来
る。
物質（Ic）を含む分画を濃縮後、セフアデツク
スＧ−15の500mlの充填したカラムにかけ水で展
開した。薄層クロマトグラフイーで物質（Ic）の
みを含む分画を集め濃縮乾固して73mgの白色粉末
として物質（Ic）を得た。
マススペクトル（SIMS）：（Ｍ＋１）+ ｍ／ｚ
338 1H−NMRスペクトル（D2O、pD3）：
δ0.94（ｔ）：α−アミノ酪酸のCH3、δ1.28(d)：
AMPBのＰ−CH3、δ1.39(d)：アラニンのCH3、
δ1.6〜1.9（ｍ）及びδ2.0〜2.2（ｍ）：AMPBの２
個のCH2及びα−アミノ酪酸のCH2、δ4.05
（ｔ）：AMPBのCH、δ4.22（dd）：α−アミノ
酪酸のCH、δ4.37（ｑ）：アラニンのCH。
本物質（Ic）は、６規定塩酸中100℃、18時間
加水分解すると、AMPB、アラニン及びα−ア
ミノ酪酸の三種のアミノ酸を検出した（アミノ酸
分析、薄層クロマトグラフイー）。また高速液体
クロマトグラフイーの分析で保持時間11.3分を示
した。本物質（Ic）はアミノ酸分析で保持時間41
分を示した。
呈色反応はニンヒドリン、ライドンスミス、ハ
ーネス反応に陽性であつた。
元素分析値：C42.45、H7.03、N12.10、O28.39
％
分子式C12H24N3O6Pとしての理論値：C42.73、
H7.17、N12.46、O28.46％。
実施例 ４
AMPB−Ala−Val物質（Id）の製造
実施例３で用いたダイヤイオンHP−20のカラ
ムで物質（Ic）の溶出され終つた後、20％メタノ
ールで溶出すると物質（Ic）より更に薄層クロマ
トグラフイーのRf値の大きい成分として物質
（Id）（Rf＝0.78）が溶出されてくる。
物質（Id）を含む分画を集めて濃縮後セフアデ
ツクスＧ−15 500mlのカラムにかけ水で展開し
た。薄層クロマトグラフイーで物質（Id）のみを
含む分画を集めて濃縮乾固すると87mgの白色粉末
として物質（Id）が得られた。
マススペクトル（SIMS）（Ｍ＋１）+ ｍ／ｚ
352 1H−NMRスペクトル（D2O、pD3）：
δ0.93（d2組）：パリンの２個のCH3、δ1.26(d)：
AMPBのＰ−CH3、δ1.39(d)：アラニンのCH3、
δ1.55〜1.75（ｍ）及びδ2.0〜2.2（ｍ）：AMPBの
２個のCH2及びバリンのβ−CH、δ4.05（ｔ）：
AMPBのCH、δ4.17(d)：バリンのα−CH、
δ4.41：（ｑ）アラニンのCH。
本物質（Id）は６規定塩酸中100℃、18時間加
水分解すると、AMPB、アラニン及びバリンの
三種のアミノ酸を検出した（アミノ酸分析、薄層
クロマトグラフイー）。
また高速液体クロマトグラフイーの分析で保持
時間25.0分を示した。本物質（Id）はアミノ酸分
析で保持時間44分を示した。
呈色反応はニンヒドリン、ライドンスミス、ハ
ーネス反応に陽性であつた。
元素分析値：C44.12、H7.38、N11.55、O27.20
％。
分子式C13H26N3O6Pとしての理論値：C44.44、
H7.46、N11.96、O27.32％。
実施例 ５
AMPB−Ala−Ser物質（Ie）の製造
実施例１(ロ)のダウエツクス１×２のカラムクロ
マトグラフイーで0.3規定酢酸溶出分画のうち、
物質（Ia）の溶出された後の分画に高速液体クロ
マトグラフイーで保持時間4.3分を示す成分とし
て物質（Ie）が溶出された。
物質（Ie）を含む分画を集め濃縮した後、ダイ
ヤイオンHP−20 400mlのカラムにかけ水で展開
溶出した。高速液体クロマトグラフイーで物質
（Ie）を主として含む分画を集めて濃縮乾固する
と白色粉末220mgが得られた。
この粉末を水10mlに溶解しセフアデツクスＧ−
15 １のカラムにかけ水で展開し物質（Ie）の
みを含む分画を集めて濃縮乾固すると物質（Ie）
の白色粉末70mgが得られた。
マススペクトル（SIMS）：（Ｍ＋１）+ ｍ／ｚ
340 1H−NMRスペクトル（D2O、pD6）：
δ1.26(d)：AMPBのＰ−CH3、δ1.44(d)：アラニ
ンのCH3、δ1.6〜1.8（ｍ）及びδ2.0〜2.2（ｍ）：
AMPBの２個のCH2、δ3.84(d)：セリンのCH2、
δ4.08（ｔ）：AMPBのCH、δ4.28（ｔ）：セリン
のCH、δ4.44（ｑ）：アラニンのCH。
本物質（Ie）は６規定塩酸中100℃、18時間加
水分解すると、AMPB、アラニン及びセリンの
三種のアミノ酸を検出した（アミノ酸分析、薄層
クロマトグラフイー）。また高速液体クロマトグ
ラフイーの分析で保持時間4.3分を示した。
本物質（Ie）はアミノ酸分析で保持時間28分を
示した。
呈色反応はニンヒドリン、ライドンスミス、ハ
ーネス反応に陽性であつた。
元素分析値：C38.66、H6.51、N12.07、O32.95
％
分子式C11H22N3O7Pとしての理論値：C38.94、
H6.54、N12.38、O33.01％。
実施例 ６
AMPB−Ala−Ala−AMPB物質（If）の製造
実施例１(ロ)のダウエツクス１×２のカラムにお
いて0.3規定酢酸により物質（Ia）〜（Ie）が溶
出され終つた後、２規定の酢酸で溶出すると高速
液体クロマトグラフイーで保持時間6.4分を示す
成分として物質（If）が溶出されてくる。
物質（If）を含む分画を集めて濃縮し、そのま
まダイヤイオンHP−20の400mlのカラムにかけ
水で展開溶出した。
物質（If）を含む分画を集め濃縮乾固すると
120mgの白色粉末が得られた。更にこの粉末を水
５mlに溶解しセフアデツクスＧ−15の500mlのカ
ラムにかけ水で展開し、高速液体クロマトグラフ
イーで（If）のみを含む分画を集め濃縮乾固する
と物質（If）の白色粉末55mgが得られた。
マススペクトル（SIMS）：（Ｍ＋１）+ ｍ／ｚ
487 1H−NMRスペクトル（D2O、pD6）：
δ1.17(d)及びδ1.21(d)：２個のAMPBのＰ−CH3
（２個分）、δ1.36（２組のｄ）：２個のアラニン
のCH3（２個分）、δ1.4〜1.7（ｍ）及びδ1.7〜2.1
（ｍ）：２個のAMPBのCH2（４個分）、δ4.0（ｔ）
及びδ4.10（ｔ）：２個のAMPBのCH（２個分）、
δ4.28（ｑ）及びδ4.31（ｑ）：２個のアラニンの
CH（２個分）。
本物質（If）は６規定塩酸中100℃、18時間加
水分解すると、AMPBとアラニンの二種のアミ
ノ酸のみを検出した（アミノ酸分析、薄層クロマ
トグラフイー）。また、高速液体クロマトグラフ
イーの分析で保持時間6.4分を示した。
本物質（If）はアミノ酸分析で保持時間14分を
示した。
呈色反応はニンヒドリン、ライドンスミス、ハ
ーネス反応に陽性であつた。
元素分析値：C39.38、H6.55、N11.09、O29.41
％
分子式C16H32N4O9P2としての理論値：C39.51、
H6.63、N11.52、O29.60％。
試験例 １
メヒシバ等の除草試験
畑土壌をつめた直径６cmのプラスチツクポツト
に、メヒシバ、シロザ、またはカヤツリグサの種
子を播き、草高20cmの時に、水溶液として
AMPB−Gly−Ala物質（Ia）またはSF−1293物
質の所定量（第１表に表示）を茎葉全体に散布処
理して施用した。水溶液散布量は10／アールと
し、展着剤としてポリオキシエチレンアルキルア
リールエーテルを0.1％になるように水溶液中に
添加した。
殺草効果は、処理後６日および14日に観察によ
り調査し、対照（無処理）との％で算定した。
試験結果を第１表に示す。[Table] These compounds were found to have excellent herbicidal activity. Therefore, a compound of general formula () can be used as a herbicide containing this as an active ingredient,
This herbicide can contain carriers and adjuvants commonly used in agricultural chemicals. Furthermore, when the compound of the present invention represented by the general formula () is hydrolyzed, it can be obtained by the following formula: L-2-amino-4-[(hydroxy)
(Methyl)phosphinoyl]butyric acid (hereinafter referred to as L-
This L-AMPB is useful as a herbicide (JP-A-48-85538, JP-A-49-31890 and JP-A-54
-Refer to Publication No. 92628). The bacterium producing the compound of the present invention of general formula () is SF-
Since it is the same as the above-mentioned strain SF-1293 which is a producing strain of substance 1923, the culture solution of strain SF-1923 contains the compound of the present invention represented by the general formula () and the substance of strain SF-1293. Therefore, without separating and purifying the SF-1293 substance from the culture solution of the bacteria producing the compound of the present invention of the general formula (), the culture solution can be subjected to known hydrolysis methods such as alkaline decomposition, acid decomposition, enzymatic decomposition, etc. or by hydrolysis using microbial cultures.
It is possible to produce L-AMPB in high yield. Thus, the compound of the present invention represented by the general formula () is also useful as a raw material for producing L-AMPB, which is effective as a herbicide. Example 1 Production of AMPB-Gly-Ala substance (Ia) (a) Streptomyces hygroscopicus SF
−1293 strain (FERM-BP 130) was mixed with 2.0% starch, 1.0% peptone, 0.3% meat extract, and dipotassium phosphate.
Inoculated into liquid medium 15 with 0.05%, PH7.0, and incubated at 28°C.
Culture with aeration and agitation for 24 hours, and use this as a seed mother. Glucose 3.0%, starch syrup 1.0%, wheat germ 2.5
% Soluble Vegetable Protein
The seed mother was inoculated into a liquid medium 200 containing 0.5% soybean oil, 0.1% soybean oil, 0.1% yeast extract, 0.001% ferrous sulfate, 0.0001% nickel chloride, 0.0001% cobalt chloride, and PH7.0, and incubated at 28°C for 96 hours. Culture was carried out with aeration and stirring. Pass the culture solution at PH3 to obtain a solution of 150 (culture titer 110 mcg/ml). The liquid is passed through a column (7.5) filled with activated carbon and subsequently washed with 30 g of water. Combine the passing liquid and washing liquid (180), Dowex 50W x
2 (50-100 mesh) (H type) 9 resin tower to adsorb the active ingredient. After washing the resin tower with water,
Elute with 0.05N aqueous ammonia. Activity category (45
) was concentrated under reduced pressure to obtain 50 g of pale yellowish brown coarse powder (potency
200 mcg/mg). (b) 10 g of the above crude powder was dissolved in 50 ml of water and passed through a column packed with 1 x 2 Dowex (acetic acid form) to adsorb the target substance, and the column was washed with 2 parts of water. Next, it was eluted with 0.3N acetic acid 6 and fractionated into 100ml portions. Thin layer chromatography using cellulose plates (Developing agent: n-butanol)
Acetic acid-water (2:1:1) showed Rf0.60, and high performance liquid chromatography (Waters 6000)
Model, column: Toyo Soda LS410, mobile phase: 0.05M
Fractions containing substance (Ia) exhibiting a retention time of 5.9 minutes in phosphate buffer (PH2.5, detection: 210 nm) were collected and concentrated to dryness to obtain 0.85 g of powder. This powder was dissolved in 5 ml of water, passed through a column filled with 400 ml of nonionic adsorption resin Diaion HP20, developed with water, and fractionated into 10 ml portions. Fractions containing only substance (Ia) were collected by thin layer chromatography using a cellulose plate and high performance liquid chromatography and concentrated to dryness to obtain 150 mg of white powder of substance (Ia). Mass spectrum (SIMS): (M+1) + m/z
310 1 H-NMR spectrum (D 2 O, pD3):
δ1.24(d): P-CH 3 of AMPB, δ1.36(d): CH 3 of alanine, δ1.55-1.75 (m) and δ1.95-2.15
(m): 2 CH 2 of AMPB, δ3.96 (q): CH 2 of glycine, δ4.06 (t): CH of AMPB, δ4.29
(q): CH of alanine. This substance (Ia) was prepared by diluting it in 6N hydrochloric acid at 100°C.
When hydrolyzed for 18 hours, AMPB,
Three types of amino acids, glycine and alanine, were detected (amino acid analysis, thin layer chromatography).
In addition, high performance liquid chromatography analysis showed a retention time of 5.9 minutes. This substance (Ia) was analyzed using amino acid analysis (Ato KK amino acid analyzer MLC-703 model).
(eluent pH 2.5) showed a retention time of 39 minutes (at this time, the SF-1293 substance showed a retention time of 35 minutes). Color reactions are positive for ninhydrin, Lydon Smith, and Harness reactions. Elemental analysis values: C38.71, H6.56, N13.38, O31.13
%. Theoretical value as molecular formula C 10 H 20 N 3 O 6 P: C38.83,
H6.52, N13.59, O31.04%. Example 2 Production of AMPB-Ala-Gly substance (Ib) Among the fractions eluted with 0.3 N acetic acid from the Dowex 1×2 column in Example 1 (b), a high-performance liquid was used before the fraction containing substance (Ia). The presence of substance (Ib) was observed as a component exhibiting a retention time of 4.5 minutes by chromatography. Fractions containing substance (Ib) were collected and concentrated to dryness to obtain 3.8 g of light brown powder. Dissolve this powder in 10ml of water and use Diaion HP.
The column was passed through a column packed with -20-1 and equilibrated with 0.02N hydrochloric acid, and further developed and eluted with 0.02N hydrochloric acid. Detected by high performance liquid chromatography, the fraction containing substance (Ib) was concentrated to about 5 ml, and then added to cellulose powder (Funakoshi Pharmaceutical Co., Ltd., Avicel) 5
g was added thereto, and the mixture was concentrated to dryness. Separately, a column packed with Avicel powder 1 swollen with n-butanol-acetic acid-water-acetic acid-n-butyl (4:1:1:1) was prepared, and Avicel containing the above-mentioned substance (Ib) was prepared. The powder was placed on the plate and developed and eluted with the same solvent. Fractions containing almost only substance (Ib) were collected using high-performance liquid chromatography and concentrated to dryness, yielding 170 mg of white powder. Dissolve this powder in 5ml of water and use Diaion HP.
The mixture was applied to a column packed with 400 ml of -20 and developed and eluted with water. Fractions containing only substance (Ib) were collected by high performance liquid chromatography and concentrated to dryness to obtain 45 mg of white powder of substance (Ib). Mass spectrum (SIMS): (M+1) + m/z
310 1 H-NMR spectrum (D 2 O, pD1):
δ1.43(d): CH3 of alanine, δ1.52(d): P- CH3 of AMPB, δ1.8-2.0 (m) and δ2.05-2.25
(m): 2 CH 2 of AMPB, δ4.0 (q): CH 2 of glycine, δ4.10 (t): CH of AMPB, δ4.42
(q): CH of alanine. When this substance (Ib) was hydrolyzed in 6N hydrochloric acid at 100°C for 18 hours, three amino acids, AMPB, glycine, and alanine, were detected in the hydrolyzate (amino acid analysis, thin layer chromatography). Also,
Retention time in high performance liquid chromatography analysis
It showed 4.5 minutes. This substance (Ib) showed a retention time of 40 minutes in amino acid analysis. Color reactions are positive for ninhydrin, Lydon Smith, and Harness reactions. Elemental analysis values: C38.67, H6.48, N13.27, O30.96
%. Theoretical value as molecular formula C 10 H 20 N 3 O 6 P: C38.83,
H6.52, N13.59, O31.04%. Example 3 Production of AMPB-Ala-ABA substance (Ic) 10 g of the crude powder obtained in Example 1 (a) was dissolved in 50 ml of water, passed through a Diaion HP-20 1 column, developed and eluted with water. did. After SF-1293 substance, Substance (Ia), Substance (Ib), etc. have been eluted, they are further developed and eluted with water.Thin layer chromatography shows a component with a larger Rf value than SF-1293 substance (Rf0.65). Substance (Ic) (Rf=0.77) is eluted as After concentrating the fraction containing substance (Ic), it was applied to a column packed with 500 ml of Sephadex G-15 and developed with water. Fractions containing only substance (Ic) were collected by thin layer chromatography and concentrated to dryness to obtain substance (Ic) as 73 mg of white powder. Mass spectrum (SIMS): (M+1) + m/z
338 1 H-NMR spectrum (D 2 O, pD 3 ):
δ0.94(t): CH3 of α-aminobutyric acid, δ1.28(d):
P-CH 3 of AMPB, δ1.39(d): CH 3 of alanine,
δ1.6~1.9 (m) and δ2.0~2.2 (m): AMPB 2
CH 2 and α-aminobutyric acid CH 2 , δ4.05
(t): CH of AMPB, δ4.22(dd): CH of α-aminobutyric acid, δ4.37(q): CH of alanine. When this substance (Ic) was hydrolyzed in 6N hydrochloric acid at 100°C for 18 hours, three amino acids, AMPB, alanine, and α-aminobutyric acid, were detected (amino acid analysis, thin layer chromatography). In addition, high performance liquid chromatography analysis showed a retention time of 11.3 minutes. This substance (Ic) has a retention time of 41 in amino acid analysis.
The minutes were shown. Color reactions were positive for ninhydrin, Lydon Smith, and Harness reactions. Elemental analysis values: C42.45, H7.03, N12.10, O28.39
% Theoretical value as molecular formula C 12 H 24 N 3 O 6 P: C42.73,
H7.17, N12.46, O28.46%. Example 4 Production of AMPB-Ala-Val substance (Id) After the substance (Ic) has been eluted with the Diaion HP-20 column used in Example 3, the substance (Ic) is eluted with 20% methanol. Furthermore, substance (Id) (Rf=0.78) is eluted as a component with a large Rf value in thin layer chromatography. Fractions containing substance (Id) were collected and concentrated, then applied to a 500 ml column of Sephadex G-15 and developed with water. Fractions containing only substance (Id) were collected by thin layer chromatography and concentrated to dryness, yielding 87 mg of substance (Id) as a white powder. Mass spectrum (SIMS) (M+1) + m/z
352 1 H-NMR spectrum (D 2 O, pD3):
δ0.93 (d2 set): Palin's two CH 3 , δ1.26(d):
P-CH 3 of AMPB, δ1.39(d): CH 3 of alanine,
δ1.55-1.75 (m) and δ2.0-2.2 (m): two CH 2 of AMPB and β-CH of valine, δ4.05 (t):
CH of AMPB, δ4.17(d): α-CH of valine,
δ4.41: (q) CH of alanine. When this substance (Id) was hydrolyzed in 6N hydrochloric acid at 100°C for 18 hours, three amino acids, AMPB, alanine, and valine, were detected (amino acid analysis, thin layer chromatography). In addition, high performance liquid chromatography analysis showed a retention time of 25.0 minutes. This substance (Id) showed a retention time of 44 minutes in amino acid analysis. Color reactions were positive for ninhydrin, Lydon Smith, and Harness reactions. Elemental analysis values: C44.12, H7.38, N11.55, O27.20
%. Theoretical value as molecular formula C 13 H 26 N 3 O 6 P: C44.44,
H7.46, N11.96, O27.32%. Example 5 Production of AMPB-Ala-Ser substance (Ie) Among the fractions eluted with 0.3 N acetic acid in the Dowex 1×2 column chromatography of Example 1 (b),
In the fraction after substance (Ia) had been eluted, substance (Ie) was eluted as a component exhibiting a retention time of 4.3 minutes by high performance liquid chromatography. Fractions containing substance (Ie) were collected and concentrated, then applied to a 400 ml Diaion HP-20 column and eluted with water. Fractions mainly containing substance (Ie) were collected using high performance liquid chromatography and concentrated to dryness to obtain 220 mg of white powder. Dissolve this powder in 10ml of water and use Cephadex G-
15 Pour into column 1, develop with water, collect fractions containing only substance (Ie), and concentrate to dryness to form substance (Ie).
70 mg of white powder was obtained. Mass spectrum (SIMS): (M+1) + m/z
340 1 H-NMR spectrum (D 2 O, pD6):
δ1.26(d): P-CH 3 of AMPB, δ1.44(d): CH 3 of alanine, δ1.6-1.8 (m) and δ2.0-2.2 (m):
Two CH 2 of AMPB, δ3.84(d): CH 2 of serine,
δ4.08(t): CH of AMPB, δ4.28(t): CH of serine, δ4.44(q): CH of alanine. When this substance (Ie) was hydrolyzed in 6N hydrochloric acid at 100°C for 18 hours, three types of amino acids, AMPB, alanine, and serine, were detected (amino acid analysis, thin layer chromatography). In addition, high performance liquid chromatography analysis showed a retention time of 4.3 minutes. This substance (Ie) showed a retention time of 28 minutes in amino acid analysis. Color reactions were positive for ninhydrin, Lydon Smith, and Harness reactions. Elemental analysis values: C38.66, H6.51, N12.07, O32.95
% Theoretical value as molecular formula C 11 H 22 N 3 O 7 P: C38.94,
H6.54, N12.38, O33.01%. Example 6 Production of AMPB-Ala-Ala-AMPB substance (If) After substances (Ia) to (Ie) were eluted with 0.3N acetic acid in the Dowex 1×2 column of Example 1 (b), 2 When eluted with the specified acetic acid, a substance (If) is eluted as a component with a retention time of 6.4 minutes in high performance liquid chromatography. Fractions containing the substance (If) were collected, concentrated, and directly applied to a 400 ml column of Diaion HP-20, developed and eluted with water. When the fractions containing the substance (If) are collected and concentrated to dryness,
120 mg of white powder was obtained. Further, this powder was dissolved in 5 ml of water, applied to a 500 ml column of Cephadex G-15, developed with water, and fractions containing only (If) were collected using high-performance liquid chromatography and concentrated to dryness, resulting in a white powder of substance (If). 55 mg was obtained. Mass spectrum (SIMS): (M+1) + m/z
487 1 H-NMR spectrum (D 2 O, pD6):
δ1.17(d) and δ1.21(d): P-CH 3 of two AMPBs
(2 pieces), δ1.36 (2 sets of d): CH 3 of 2 alanines (2 pieces), δ1.4-1.7 (m) and δ1.7-2.1
(m): 2 AMPB CH 2 (4 pieces), δ4.0 (t)
and δ4.10(t): CH of 2 AMPBs (2 pieces),
δ4.28(q) and δ4.31(q): of two alanines
CH (for 2 pieces). When this substance (If) was hydrolyzed in 6N hydrochloric acid at 100°C for 18 hours, only two amino acids, AMPB and alanine, were detected (amino acid analysis, thin layer chromatography). In addition, high performance liquid chromatography analysis showed a retention time of 6.4 minutes. This substance (If) showed a retention time of 14 minutes in amino acid analysis. The color reaction was positive for ninhydrin, Lydon Smith, and harness reactions. Elemental analysis values: C39.38, H6.55, N11.09, O29.41
% Theoretical value as molecular formula C 16 H 32 N 4 O 9 P 2 : C39.51,
H6.63, N11.52, O29.60%. Test example 1 Weed control test for crabgrass, etc. Seeds of crabgrass, cypress, or cyperus were sown in plastic pots with a diameter of 6 cm filled with field soil, and when the plant height was 20 cm, the seeds were sown as an aqueous solution.
A predetermined amount of AMPB-Gly-Ala substance (Ia) or SF-1293 substance (shown in Table 1) was applied by spraying the entire stem and leaves. The amount of aqueous solution sprayed was 10/R, and polyoxyethylene alkylaryl ether was added as a spreading agent to the aqueous solution at a concentration of 0.1%. The herbicidal effect was investigated by observation on 6 and 14 days after treatment, and calculated as a percentage of the control (untreated). The test results are shown in Table 1.
【表】
試験例 ２
ノビエ除草試験
畑土壌をつめた直径６cmのプラスチツクポツト
に、ノビエの種子を播き、草高25cmの時に、水溶
液としたAMPB−Gly−Ala物質（Ia）または
AMPB−Ala−Ala−AMPB物質（If）または、
SF−1293物質の、所定量（第２表に表示）を茎
葉全体に散布処理して施用した。水溶液散布量は
10／アールとし、展着剤として、ポリオキシエ
チレンアルキルアリールエーテルを0.1％になる
ように水溶液中に添加した。試験は４連制で行な
つた。
殺草効果は処理後14日に観察により調査し、対
照（無処理）との％で算定した。
試験結果を第２表に示す。[Table] Test example 2 Wild grass weeding test Wild grass seeds were sown in plastic pots with a diameter of 6 cm filled with field soil, and when the plant height was 25 cm, the AMPB-Gly-Ala substance (Ia) or the aqueous solution was applied.
AMPB−Ala−Ala−AMPB substance (If) or
A predetermined amount (shown in Table 2) of SF-1293 substance was applied by spraying the entire stem and leaves. The amount of aqueous solution sprayed is
10/R, and polyoxyethylene alkylaryl ether was added as a spreading agent to the aqueous solution at a concentration of 0.1%. The test was conducted in four consecutive sessions. The herbicidal effect was investigated by observation 14 days after treatment, and calculated as a percentage of the control (untreated). The test results are shown in Table 2.
Claims (1)
（） 〔式中、R1およびR2は夫々に水素、メチル基、
エチル基、イソプロピル基またはハイドロキシメ
チル基を示し、R3は基−OHまたは基
【式】を示し、ただし R3が基−OHであるときR1とR2が共にメチル基
の場合は除く〕で表わされる物質の生産菌を培養
し、一般式（）の物質を培養物から採取するこ
とを特徴とする、一般式（）の含燐ペプチド化
合物の製造法。[Claims] 1. The following general formula () belonging to the genus Streptomyces: [In the formula, R 1 and R 2 are hydrogen, methyl group,
Represents an ethyl group, isopropyl group, or hydroxymethyl group, R 3 represents a group -OH or a group [formula], except when R 3 is a group -OH and R 1 and R 2 are both methyl groups] 1. A method for producing a phosphorus-containing peptide compound of the general formula (), which comprises culturing a microorganism producing the substance represented by the formula () and collecting the substance of the general formula () from the culture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7870684A JPS60222498A (en) | 1984-04-20 | 1984-04-20 | Novel phosphorus-containing peptide compound and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7870684A JPS60222498A (en) | 1984-04-20 | 1984-04-20 | Novel phosphorus-containing peptide compound and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60222498A JPS60222498A (en) | 1985-11-07 |
| JPH0419839B2 true JPH0419839B2 (en) | 1992-03-31 |
Family
ID=13669305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7870684A Granted JPS60222498A (en) | 1984-04-20 | 1984-04-20 | Novel phosphorus-containing peptide compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60222498A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3544375A1 (en) * | 1985-12-14 | 1987-06-19 | Hoechst Ag | DI- AND TRIPEPTIDES WITH N-TERMINAL PHOSPHINOTHRICIN, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51639A (en) * | 1974-06-20 | 1976-01-06 | Matsushita Electric Ind Co Ltd | DENATSU CHOSEI KAIRO |
-
1984
- 1984-04-20 JP JP7870684A patent/JPS60222498A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51639A (en) * | 1974-06-20 | 1976-01-06 | Matsushita Electric Ind Co Ltd | DENATSU CHOSEI KAIRO |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60222498A (en) | 1985-11-07 |
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