CN103755561B - β-Japan cypress phenolic ester or salt and preparing the application in animal feedstuff additive - Google Patents
β-Japan cypress phenolic ester or salt and preparing the application in animal feedstuff additive Download PDFInfo
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- CN103755561B CN103755561B CN201410013453.8A CN201410013453A CN103755561B CN 103755561 B CN103755561 B CN 103755561B CN 201410013453 A CN201410013453 A CN 201410013453A CN 103755561 B CN103755561 B CN 103755561B
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- japan cypress
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- -1 phenolic ester Chemical class 0.000 title claims abstract description 36
- 241000218691 Cupressaceae Species 0.000 title claims abstract description 24
- 241001465754 Metazoa Species 0.000 title claims abstract description 15
- 239000000654 additive Substances 0.000 title claims abstract description 12
- 230000000996 additive effect Effects 0.000 title claims abstract description 10
- 150000003839 salts Chemical class 0.000 title abstract description 11
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 241000287828 Gallus gallus Species 0.000 claims description 7
- 241000283690 Bos taurus Species 0.000 claims description 4
- 241000251468 Actinopterygii Species 0.000 claims description 2
- 241000272525 Anas platyrhynchos Species 0.000 claims description 2
- 241000272814 Anser sp. Species 0.000 claims description 2
- 241000238557 Decapoda Species 0.000 claims description 2
- 241001508687 Mustela erminea Species 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims description 2
- 241000282485 Vulpes vulpes Species 0.000 claims description 2
- 230000003698 anagen phase Effects 0.000 claims description 2
- 235000015278 beef Nutrition 0.000 claims description 2
- 239000007952 growth promoter Substances 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011701 zinc Substances 0.000 abstract description 9
- 229910052725 zinc Inorganic materials 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 239000010949 copper Substances 0.000 abstract description 8
- 239000011777 magnesium Substances 0.000 abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011575 calcium Substances 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000011591 potassium Substances 0.000 abstract description 6
- 229910052700 potassium Inorganic materials 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 239000011572 manganese Substances 0.000 abstract description 5
- 230000012010 growth Effects 0.000 abstract description 4
- 244000144977 poultry Species 0.000 abstract description 3
- 239000003630 growth substance Substances 0.000 abstract description 2
- 244000144972 livestock Species 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 14
- 235000002639 sodium chloride Nutrition 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- TUFYVOCKVJOUIR-UHFFFAOYSA-N alpha-Thujaplicin Natural products CC(C)C=1C=CC=CC(=O)C=1O TUFYVOCKVJOUIR-UHFFFAOYSA-N 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 229930007845 β-thujaplicin Natural products 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000012430 stability testing Methods 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940072335 vancocin Drugs 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/717—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups a keto group being part of a seven- to twelve-membered ring
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/111—Aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses β-Japan cypress phenolic ester or salt and preparing the application in animal feedstuff additive.β-Japan cypress phenolic ester or salt compound, its structural formula is such as formula shown in 1 or formula 2: R in formula 1
1for n-nonyl or n-heptadecane base, in formula 2, L is sodium, potassium, calcium, magnesium, zinc, copper or manganese.Of the present invention such as formula the β-Japan cypress phenolic ester shown in 1 and formula 2 and salt compound to livestock and poultry low toxicity or nontoxic, it covers than current patent, and related compound has higher security, more stable and stronger growth promotes performance, therefore be more suitable for as animal fowl growth regulator, in cultivation industry, there is extraordinary application prospect.
Description
Technical field:
The invention belongs to animal feeding growth stimulant field, be specifically related to β-Japan cypress phenolic ester or salt and preparing the application in animal feedstuff additive.
Background technology:
β-chamenol (β-hinokitiol), have another name called the names such as chamaecypariol, Hinokitiol, Hinokitiol (phenol), chemical name: 2-hydroxyl-4-sec.-propyl-1-tropone is natural edible essential oil component, is used as foodstuff additive for many years in Japan.
US6387417B1 has open β-chamenol and the enterococcal activity of title complex (2:1 or 3:1) anti-vancocin resistance thereof and application in the treatment thereof.
Chinese patent CN101396021A(publication number) describe hinokitiol and metal-salt thereof the activity for plant pathogenic microorganisms, but the structure of not concrete openly salt, whether comprise title complex undeclared.In addition hinokitiol comprise α-, β-, γ-3 isomerss, the structure of their salt is also different.
β-chamenol does the Vitro Experimental Results of fodder additives application separately to have paper to report.
But β-chamenol has thermolability and photo-labile.Therefore how to obtain high stability (heat, light stability), greater security, and the compound with extraordinary growth-promoting effect β-chamenol is anxious to be studied.
Summary of the invention:
The object of this invention is to provide have more high stability, security can promote growth of animals or poultry, be more suitable for the β-Japan cypress phenolic ester as the stabilization of fodder additives application and salt compound.
β-Japan cypress the phenolic ester of stabilization of the present invention and salt compound, its structural formula is such as formula shown in 1 or formula 2:
formula 1, wherein R
1for n-nonyl or n-heptadecane base;
formula 2, wherein L is sodium, potassium, calcium, magnesium, zinc, copper or manganese.
Described L is preferably manganese, copper, zinc or magnesium.
Second object of the present invention is to provide above-mentioned β-Japan cypress phenolic ester and salt compound is preparing the application in animal feedstuff additive.
Described animal feedstuff additive refers to animal growth promoter.
Described animal is the pig of each growth phase, chicken, duck, goose, beef cattle, milk cow, sheep, fish, shrimp, fox, the cultivated animals such as ermine or racoon dog.
Described β-Japan cypress phenolic ester and salt compound, its additive capacity in animal-feed is 0.1 ~ 200ppm.
Described animal-feed can be perfect compound feed.
Of the present invention such as formula the β-Japan cypress phenolic ester shown in 1 and formula 2 and salt compound to livestock and poultry low toxicity or nontoxic, it covers than current patent, and related compound has higher security, more stable and stronger growth promotes performance, therefore be more suitable for as animal fowl growth regulator, in cultivation industry, there is extraordinary application prospect.
Accompanying drawing illustrates:
Fig. 1 is the HPLC figure of 3-sec.-propyl-1,3, the 5-cycloheptatriene-7-ketone-positive ester in the last of the ten Heavenly stems of embodiment 2;
Fig. 2 is the HPLC figure of 3-sec.-propyl-1,3, the 5-cycloheptatriene-7-ketone zinc of embodiment 8.
Embodiment:
Following examples further illustrate of the present invention, instead of limitation of the present invention.
formula 1, wherein: R
1methyl, n-nonyl, n-heptadecane base
Embodiment 1:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-ethyl ester
Preparation process:
2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (1.64g, 10mmol, 1eq) and triethylamine (1 ~ 10eq) are dissolved in 100ml methylene dichloride,-10 DEG C ~ 25 DEG C, get Acetyl Chloride 98Min. (0.8 ~ 5eq) to be dissolved in about 10ml methylene dichloride, be slowly added drop-wise in this mixing solutions, then insulated and stirred 3 ~ 8 hours, TLC(developping agent sherwood oil: ethyl acetate=5:1) show raw material primitive reaction completely, have and newly put generation.Add about 100ml water extracting and demixing, organic phase washes with water once again.Organic phase is revolved and is steamed desolventizing, obtains red-brown oily matter, and HNMR turns out to be target product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-ethyl ester), yield about 86%., in put procedure, there is Ester hydrolysis in instability.
3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-ethyl ester: δ H (DMSO, 500MHz) 7.126 ~ 7.251 (4H, m),
2.812～2.866(1H,m),2.257(3H,s),1.162～1.176(6H,d).
Embodiment 2:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-positive ester in the last of the ten Heavenly stems
Preparation process:
2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (3.28g, 20mmol, 1eq) and triethylamine (1 ~ 10eq) are dissolved in 100ml methylene dichloride,-10 DEG C ~ 25 DEG C, get positive decanoyl chloride (0.8 ~ 5eq) to be dissolved in about 10ml methylene dichloride, be slowly added drop-wise in this mixing solutions, then insulated and stirred 3 ~ 8 hours, TLC(developping agent sherwood oil: ethyl acetate=5:1) show a small amount of raw material and do not react completely, have and newly put generation.Add 100 ml water washings, then use saturated common salt water washing, TLC shows initial point place still has fluorescence.With the washing of rare potassium hydroxide aqueous solution, raw material point is still washed endless.Add about 8 grams of silica gel, dry method loading, silicagel column is separated, and eluent is sherwood oil: ethyl acetate: triethylamine=5:1:0.02.Obtain pure product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-positive the last of the ten Heavenly stems ester), purity is 99.4%.HPLC figure as shown in Figure 1.3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-positive ester in the last of the ten Heavenly stems: δ H (DMSO, 500MHz) 7.131 ~ 7.251 (4H, m), 2.824 ~ 2.878 (1H, m), 2.534 ~ 2.563 (1H, m), 1.590 ~ 1.649 (2H, m), 1.174 ~ 1.371 (18H, m), 0.843 ~ 0.857 (3H, m).
Embodiment 3:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-positive octadecyl ester
Preparation process:
2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (3.28g, 20mmol, 1eq) and triethylamine (1 ~ 10eq) are dissolved in 100ml methylene dichloride,-10 DEG C ~ 25 DEG C, get positive octadecanoyl chlorine (0.8 ~ 5eq) to be dissolved in about 30ml methylene dichloride, be slowly added drop-wise in this mixing solutions, then insulated and stirred 3 ~ 8 hours, TLC(developping agent sherwood oil: ethyl acetate=5:1) show a small amount of raw material and do not react completely, have and newly put generation.Add 100 ml water washings, then use saturated common salt water washing, TLC shows initial point place still has fluorescence.With the washing of rare potassium hydroxide aqueous solution, raw material point is still washed endless.Add about 8 grams of silica gel, dry method loading, silicagel column is separated, and eluent is sherwood oil: ethyl acetate: triethylamine=5:1:0.02.Obtain pure product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-positive octadecyl ester), purity is 99%.
3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone-positive octadecyl ester: δ H (CDCl
3, 500MHz) and 7.132 (1H, s), 7.017 ~ 7.096 (2H, m), 6.922 ~ 6.942 (1H, d), 2.759 ~ 2.813 (1H, m), 2.596 ~ 2.626 (2H, m), 1.728 ~ 1.789 (2H, m), 1.400 ~ 1.428 (2H, m), 1.221 ~ 1.249 (32H, m), 0.856 ~ 0.883 (3H, m).
formula 2, wherein: L is sodium, potassium, calcium, magnesium, zinc
Embodiment 4:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone potassium
Potassium hydroxide (8.4g, 150mmol, 1.5eq) normal temperature is dissolved in 150ml ethanol, 2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (16.4g, 100mmol, 1eq) be dissolved in wherein, normal-temperature reaction 1 hour, reaction solution is clarified, and is cooled to room temperature gradually, does not have solid to separate out, subcooling, to-20 DEG C, does not still have solid to separate out, and continues to be cooled to-30 DEG C and separates out yellow solid, filter, solid softens rapidly as liquid.Add 8.2 grams of 2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone, stirring at room temperature revolves steaming after 1 hour to revolve matchmaker molten, then puts into baking oven and dry and obtain product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone potassium).It is 99% that HPLC shows purity.
Embodiment 5:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone sodium
Sodium hydroxide (1 ~ 5eq) normal temperature is dissolved in 100ml ethanol, 2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (16.4g, 100mmol, 1eq) is dissolved in wherein, reflux 1 ~ 5 hour, there is solid to separate out gradually, be cooled to stirring at room temperature two hours, filter, the cold washing with alcohol of filter cake, 40 DEG C of water-baths are spin-dried for solvent and obtain product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone sodium).It is 99% that HPLC shows purity
Embodiment 6:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone calcium
Potassium hydroxide (1 ~ 5eq) normal temperature is dissolved in 300ml water, naturally cools to room temperature, and 2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (16.4g, 100mmol, 1eq) is dissolved in wherein, and stirring at normal temperature is to dissolving completely.Drip the aqueous solution of 80ml calcium chloride (0.4 ~ 2eq) gradually, solid is had to separate out gradually, and become thickness, stirring at normal temperature 2 ~ 3 hours, suction strainer, filter cake use water 200ml*2 washs, pump vacuum wipe dry, then product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone calcium) is dried to obtain in 35 DEG C of baking ovens.It is 99% that HPLC shows purity
Embodiment 7:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone magnesium
Potassium hydroxide (1 ~ 5eq) normal temperature is dissolved in 300ml water, naturally cools to room temperature, and 2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (16.4g, 100mmol, 1eq) is dissolved in wherein, and stirring at normal temperature is to dissolving completely.Drip 80ml6 water gradually. the aqueous solution of magnesium chloride (0.4 ~ 2eq), solid is had to separate out gradually, and become thickness, stirring at normal temperature 2 ~ 3 hours, suction strainer, filter cake use water 200ml*2 washs, pump vacuum wipe dry, then product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone magnesium) is dried to obtain in 35 DEG C of baking ovens.It is 99% that HPLC shows purity
Embodiment 8:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone zinc
Potassium hydroxide (1 ~ 5eq) normal temperature is dissolved in 300ml water, naturally cools to room temperature, and 2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (16.4g, 100mmol, 1eq) is dissolved in wherein, and stirring at normal temperature is to dissolving completely.Drip the aqueous solution of 100ml zinc sulfate (0.4 ~ 2eq) gradually, solid is had to separate out gradually, and become thickness, stirring at normal temperature 2 ~ 3 hours, suction strainer, filter cake use water 200ml*2 washs, pump vacuum wipe dry, then product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone zinc) is dried to obtain in 35 DEG C of baking ovens.It is that 99%, HPLC schemes as shown in Figure 2 that HPLC shows purity.
Embodiment 9:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone copper
Potassium hydroxide (1 ~ 5eq) normal temperature is dissolved in 300ml water, naturally cools to room temperature, and 2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (16.4g, 100mmol, 1eq) is dissolved in wherein, and stirring at normal temperature is to dissolving completely.Drip the aqueous solution of 100ml cupric chloride (0.4 ~ 2eq) gradually, solid is had to separate out gradually, and become thickness, stirring at normal temperature 2 ~ 3 hours, suction strainer, filter cake use water 200ml*2 washs, pump vacuum wipe dry, then product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone copper) is dried to obtain in 35 DEG C of baking ovens.It is 99% that HPLC shows purity
Embodiment 10:
Structural formula:
The preparation of 3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone manganese
Potassium hydroxide (1 ~ 5eq) normal temperature is dissolved in 300ml water, naturally cools to room temperature, and 2-hydroxyl-4-sec.-propyl-2,4,6-cycloheptatriene-1-ketone (16.4g, 100mmol, 1eq) is dissolved in wherein, and stirring at normal temperature is to dissolving completely.Drip the aqueous solution of 100ml Manganous chloride tetrahydrate (0.4 ~ 2eq) gradually, solid is had to separate out gradually, and become thickness, stirring at normal temperature 2 ~ 3 hours, suction strainer, filter cake use water 200ml*2 washs, pump vacuum wipe dry, then product (3-sec.-propyl-1,3,5-cycloheptatriene-7-ketone manganese) is dried to obtain in 35 DEG C of baking ovens.It is 99% that HPLC shows purity
Embodiment 11: the heat stability test of Japan cypress phenolic ester
The different ester corn cob meals of chamenol previous embodiment prepared are formulated as the pre-mixture of final concentration massfraction 2%.Take sample to be tested (pre-mixture) respectively in crucible, process 20 hours in 100 DEG C of baking ovens after, take 1.0g sample (the parallel preparation of each sample 3 parts) and add ethanol 50ml in tool plug Erlenmeyer flask, supersound extraction 10min, with filter paper filtering, filtrate is transferred in 50ml volumetric flask, ethanol is settled to scale, shake up, get filtrate through 0.45 μm of filtering with microporous membrane, carry out HPLC analysis.
Chromatographic condition
Chromatographic column: WondasilC
18(250mm*4.6mm, 5 μm) post;
Moving phase: 100% acetonitrile or methyl alcohol-40mM ammonium acetate (pH to 4 adjusted by acetic acid) (65:35, v/v);
Determined wavelength: 220nm; Column temperature 25 DEG C; Sample size: 20 μ L; Flow velocity 1.0 or 0.8ml/min.
Stability result is in table 1, and the thermostability that result shows chamenol ten carbocyclic aliphatic acid esters and chamenol 18 carbocyclic aliphatic acid esters improves.
Table 1: the thermostability comparative result of different Japan cypress phenolic ester
| Compound | Initial content (%) | Content (%) after 100 DEG C of heating 20h |
| Chamenol | 2.0 | 0.1 |
| Chamenol ethyl ester | 2.0 | 0 |
| Chamenol ten carbocyclic aliphatic acid esters | 2.0 | 0.65 |
| Chamenol 18 carbocyclic aliphatic acid esters | 2.0 | 1.21 |
Embodiment 12: the heat stability test of Japan cypress phenates
The different metal salt corn cob meal of chamenol previous embodiment prepared is formulated as the pre-mixture of final concentration massfraction 2%.Take sample to be tested (pre-mixture) respectively in crucible, process different time in 100 DEG C of baking ovens after, take 1.0g sample (the parallel preparation of each sample 3 parts) and add ethanol 50ml in tool plug Erlenmeyer flask, supersound extraction 10min, with filter paper filtering, filtrate is transferred in 50ml volumetric flask, ethanol is settled to scale, shake up, get filtrate through 0.45 μm of filtering with microporous membrane, carry out HPLC analysis.
Chromatographic condition
Chromatographic column: WondasilC
18(250mm*4.6mm, 5 μm) post;
Moving phase: methanol-water (65:35, v/v) or methyl alcohol-0.2% acetic acid aqueous solution (65:35, v/v) or methyl alcohol-2% phosphate aqueous solution (65:35, v/v);
Determined wavelength: 220nm; Column temperature 25 DEG C; Sample size: 20 μ L; Flow velocity 0.8ml/min.
Stability result is in table 2, and the various metal-salts that result shows chamenol all improve thermostability, and wherein magnesium, copper and manganese salt improve the most remarkable.
Table 2: the heat stability test result of chamenol different metal salt
Embodiment 13: the photo-stability testing of Japan cypress phenates and ester
Japan cypress phenolic ester previous embodiment prepared or salt corn cob meal are formulated as the pre-mixture of final concentration massfraction 2%.Getting sample to be tested (pre-mixture) tiles in medicine stability test case, put after processing thing 5 days under intensity of illumination 4500-5000 lux, take 1.0g sample (the parallel preparation of each sample 3 parts) and add ethanol 50ml in tool plug Erlenmeyer flask, supersound extraction 10min, with filter paper filtering, filtrate is transferred in 50ml volumetric flask, ethanol is settled to scale, shake up, get filtrate through 0.45 μm of filtering with microporous membrane, carry out HPLC analysis.
Chromatographic condition
Chromatographic column: WondasilC
18(250mm*4.6mm, 5 μm) post;
Moving phase: methanol-water (65:35, v/v) or methyl alcohol-0.2% acetic acid aqueous solution (65:35, v/v) or methyl alcohol-2% phosphate aqueous solution (65:35, v/v);
Determined wavelength: 220nm; Column temperature 25 DEG C; Sample size: 20 μ L; Flow velocity 0.8ml/min.
Stability result is in table 3, and the light stability of result display Japan cypress phenates all improves, and wherein improves the most obvious with the light stability of manganese, copper, zinc and magnesium salts.
Table 3: the photo-stability testing result of Japan cypress phenolic ester or salt
| Compound | Initial content (%) | Intense light irradiation remains content (%) after 5 days |
| Chamenol | 2.0 | 0 |
| Chamenol sodium | 2.0 | 0.19 |
| Chamenol potassium | 2.0 | 0.08 |
| Chamenol calcium | 2.0 | 1.2 |
| Chamenol magnesium | 2.0 | 1.57 |
| Chamenol copper | 2.0 | 1.87 |
| Chamenol manganese | 2.0 | 1.87 |
| Chamenol zinc | 2.0 | 1.62 |
| Chamenol ethyl ester | 2.0 | 0 |
| Chamenol ten carbocyclic aliphatic acid esters | 2.0 | 0 |
| Chamenol 18 carbocyclic aliphatic acid esters | 2.0 | 0 |
Embodiment 14: the application of chamenol magnesium salts in broiler fodder
The fast large yellow-feathered broiler (female seedling) of 600 plumage 1 ages in days is divided into 6 treatment group at random by table 4, often organizes 100 plumages, and is often organizing in feed the Japan cypress phenates or ester that add various dose respectively.Trial period, raises in cages, free choice feeding and drinking-water.Totally 30 days trial period, weightening finish and the feedstuff-meat ratio aspect of the test chicken of result display trial period β-chamenol salt test group are all significantly improved (table 5).
The test echelon design that table 4 Japan cypress phenates or ester are applied in broiler chicken material
*: institute's additive capacity is with the content meter of β-chamenol.
The test-results that table 5 Japan cypress phenates or ester are applied in broiler chicken material
Claims (3)
1. β-Japan cypress phenolic ester is preparing the application in animal growth promoter, described β-Japan cypress phenolic ester, its structure as shown in Equation 1:
formula 1, wherein R
1for n-nonyl or n-heptadecane base.
2. application according to claim 1, is characterized in that, described animal is the pig of each growth phase, chicken, duck, goose, beef cattle, milk cow, sheep, fish, shrimp, fox, ermine or racoon dog.
3. application according to claim 1, is characterized in that, described β-Japan cypress phenolic ester, and its additive capacity in animal-feed is 0.1 ~ 200ppm.
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| CN201410013453.8A CN103755561B (en) | 2014-01-10 | 2014-01-10 | β-Japan cypress phenolic ester or salt and preparing the application in animal feedstuff additive |
| PCT/CN2014/072137 WO2015103808A1 (en) | 2014-01-10 | 2014-02-17 | Β-hinokitiol ester or salt and application thereof in preparing animal feed additive |
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| CN201410013453.8A CN103755561B (en) | 2014-01-10 | 2014-01-10 | β-Japan cypress phenolic ester or salt and preparing the application in animal feedstuff additive |
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| CN114436909B (en) * | 2022-01-26 | 2023-05-30 | 河南科技大学 | Sulfonyl sabinol derivative and preparation method and application thereof |
| WO2025202469A1 (en) * | 2024-03-28 | 2025-10-02 | Junia | Use of a derivative of hinokitiol for its fungicidal and/or bactericidal activity on fungi, oomycetes and/or pathogenic bacteria of plants and crop seeds |
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| US4361581A (en) * | 1979-08-10 | 1982-11-30 | Yasuaki Fukuda | Skin-beautifying cosmetic composition |
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| WO2004062638A1 (en) * | 2002-12-10 | 2004-07-29 | Helvederm Sa | Hinokitiol-based composition for personal hygiene care |
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