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Home > Encyclopedia > Spinosyn A

Spinosyn A

pharmaceutical raw materials
Spinosyn A structure

Spinosyn A 

structure
  • CAS No:

    131929-60-7

  • Formula:

    C41H65NO10

  • Chemical Name:

    Spinosyn A

  • Synonyms:

    1H-as-Indaceno[3,2-d]oxacyclododecin-7,15-dione,2-[(6-deoxy-2,3,4-tri-O-methyl-α-L-mannopyranosyl)oxy]-13-[[(2R,5S,6R)-5-(dimethylamino)tetrahydro-6-methyl-2H-pyran-2-yl]oxy]-9-ethyl-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-tetradecahydro-14-methyl-,(2R,3aS,5aR,5bS,9S,13S,14R,16aS,16bR)-;(2R,3aS,5aR,5bS,9S,13S,14R,16aS,16bR)-2-[(6-Deoxy-2,3,4-tri-O-methyl-α-L-mannopyranosyl)oxy]-13-[[(2R,5S,6R)-5-(dimethylamino)tetrahydro-6-methyl-2H-pyran-2-yl]oxy]-9-ethyl-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-tetradecahydro-14-methyl-1H-as-indaceno[3,2-d]oxacyclododecin-7,15-dione;A 83543A;Lepicidin A;Spinosyn A;(-)-Spinosyn A;Spinosad A

  • Categories:

    Agrochemicals  >  Insecticides

Description

ChEBI: A spinosyn in which the sugar amino and hydroxy groups are globally methylated. One of the two active ingredients of spinosad.

Spinosyn A Basic Attributes

731.96

731.96

1312995-182-4

DTXSID8037598

Light grey to white crystals

2932209090

Characteristics

111.22000

4.80

1.16±0.1 g/cm3(Predicted)

84ºC to 99.5ºC

801.5±65.0 °C(Predicted)

438.5±34.3 °C

1.540

Spinosyn A: 290 mg l -1 (pH 5); Spinosyn D: 29 mg l -1 (pH 5)

Spinosyn A: 3.2 x 10 -8 Pa Spinosyn D: 2.1 x 10 -8 Pa

Slightly stale water /Spinosad/

Forosamine at the 17-position of spinosyns A and D was hydrolyzed under mild acidic conditions to give the corresponding 17-pseudoaglycones. The tri-O-methylrhamnose at the 9-position of the 17-pseudoaglycone of spinosyn A was hydrolyzed under more vigorous acidic conditions to give the aglycone of spinosyn A. However, these conditions led to decomposition of the 17-pseudoaglycone of spinosyn D, presumably due to more facile protonation of the 5,6-double bond to produce a tertiary carbonium ion which undergoes further rearrangements. Spinosyns J and L (3'-O-demethyl spinosyn A and D, respectively) obtained from fermentation of biosynthetically-blocked mutant strains of Saccharopolyspora spinosa, were oxidized to give the corresponding 3'-keto-derivatives and the resultant keto-sugars were then beta-eliminated under basic conditions to give the 9-pseudoaglycones of spinosyns A and D respectively. Forosamine at the 17-position of the 9-pseudoaglycone of spinosyn D was then readily hydrolyzed to yield the aglycone of spinosyn D.

Safety Information

III

9

3077

SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.

|Warning|H400 (100%): Very toxic to aquatic life [Warning Hazardous to the aquatic environment, acute hazard]|P273, P391, and P501|Aggregated GHS information provided by 126 companies from 4 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.|H410: Very toxic to aquatic life with long lasting effects [Warning Hazardous to the aquatic environment, long-term hazard]

Toxicity

LD50 Rat (male) oral 3738 mg/kg /90.4% Spinosad technical/|LD50 Rat (female) oral >5000 mg/kg /90.4% Spinosad technical/|LD50 Rabbit dermal >2000 mg/kg /90.4% Spinosad technical/

Drug Information

... Dairy cows were dosed for 28 days with spinosad at rates equivalent to 0, 1, 3, and 10 ug/g in the diet. Chicken hens were dosed for 42 days with spinosad at rates equivalent to 0, 0.1, 0.3, 1, and 5 ug/g in the diet. Milk, eggs, and tissue samples were analyzed by high-performance liquid chromatography and/or immunoassay methods. Spinosad residues occurred in all of the sample types but were lowest in eggs, skim milk, and lean meat and were highest in the fat. /Spinosad/|Spinosad is rapidly absorbed and extensively metabolized. There were no major differences in the bioavailability, routes or rates of excretion, or metabolism of Spinosyn A and Spinosyn D following oral administration in rats. In addition, the routes and rates of excretion were not affected by repeated administration.

The spinosyns, a novel family of insecticidal macrocyclic lactones, are active on a wide variety of insect pests, especially lepidopterans & dipterans...& possess a mode of action that appears unique, with studies to date suggesting that both nicotinic & gamma-aminobutryic acid receptor functions are altered in a novel manner. Compared to pyrethroids such as cypermethrin, spinosyn A is slow to penetrate into insect larvae such as tobacco budworm larvae (Heliothis virescens); however, once inside the insect, spinosyn A is not readily metabolized...

Basic treatment: Establish a patent airway. Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if needed. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with normal saline during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Cover skin burns with dry sterile dressings after decontamination ... . /Poison A and B/|Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in respiratory arrest. Positive pressure ventilation techniques with a bag valve mask device may be beneficial. Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start an IV with D5W /SRP: "To keep open", minimal flow rate/. Use lactated Ringer's if signs of hypovolemia are present. Watch for signs of fluid overload. Consider drug therapy for pulmonary edema ... . For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... . Treat seizures with diazepam (Valium) ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Poison A and B/

spinosyn A

Spinosyn A Use and Manufacturing

Methods of Manufacturing

The new microorganism Saccharo-polyspora spinosa or a mutant that can produce spinosyn. The aerial mycelium is produced on the composite medium and the synthetic medium. The aerial spores are mainly pale yellowish pink, but also white, and the reverse side is yellow to yellowish brown, without obvious pigmentation. The seed culture medium for the fermentation of spinosyn polyspores is: enzymatic hydrolysis of soybean hydrolysate 3%, yeast extract 0.3%, MgSO4·H2O 0.2%, glucose 0.5%, maltose .4%, deionized water 1L, 121℃ Sterilize for 30min. The inoculation volume is 10%. The preferred carbon sources for large-scale production are glucose and maltose, and ribose, xylose, fructose, galactose, mannose, mannitol, soluble starch, potato dextrin, methyl oleate, oils, etc. can also be used. The preferred nitrogen is raffinose, peptone-based milk, and digested soybean meal. Fish meal, corn infusion, yeast extract, hydrolyzed casein, beef extract, etc. can also be used. The inorganic salts incorporated into the medium include conventional soluble salts that can produce the following ions: zinc ion, sodium ion, magnesium ion, ammonium ion, chloride ion, carbonate ion, sulfate ion, nitrate ion, etc. In addition, the culture medium should also contain the necessary trace elements needed for the growth and development of microorganisms. If there is foaming problem, soybean oil can be added to the medium to inhibit foaming. The culture temperature of spinosyn polysporum is 24-33 ℃, and the optimal temperature for producing spinosyn is 28-30 ℃. During industrial fermentation, the amount of dissolved oxygen in the tank should be maintained above 60% by aeration and stirring speed, preferably above 65%. The pressure in the tank is 0.034MPa. Separation and extraction After 7-10 days of fermentation, add equal volume of acetone, filter to remove the bacteria, adjust the pH of the filtrate to 13, resin adsorption, use 0-95% methanol: acetonitrile = 1:1 (containing 0.1% sodium acetate) The solution gradient elutes spinosyns A and D, collects the eluent in stages to obtain the spinach-containing eluent, and concentrates to obtain the spinosyn concentrate. The concentrated solution was diluted with petroleum ether, applied to a silica gel chromatography column, eluted with a gradient of petroleum ether and methanol, and collected in stages. Analysis and detection of high performance liquid chromatography (HPLC). Column: ODS-AO, liquid phase: acetonitrile/methanol/water=40/40/20 (containing 0.05% ammonium acetate), flow rate 3mL/min, detection wavelength: 250nm.

Uses

Spinosyn A is the major component of a complex of unusual, hydrophobic macrocyclic lactones isolated from Saccharopolyspora spinosa in 1991. The 12-membered macrocyclic lactone is fused to form a rare 12-5-6-5 tetracyclic ring system, with the macrocycle and the terminal cyclopentane bearing glycosides. Spinosyn A is a potent insecticide for crop pathogens and ectoparasite control on animals. The spinosyns have a unique mechanism of action involving disruption of nicotinic acetylcholine receptors.

USEPA/OPP Pesticide Code 110003; Trade Names: NAF-85(110003+110004), NAF-144(110003+110004), XDE-105, component of(with 110004), MAF-144, component of (with 110004).|Spinosad; Spinosyn A, mixt. with Spinosyn D Pesticide formulation, PC Codes 110003 & 110004; CAS Nos: 131929-63-0 & 131929-60-7

Pesticide or Metabolite (M) Common Name: Spinosad; Commodity: Cottonseed; Method Source: Dow Elanco; Method ID: RES 94025; Method Date: 8/31/94; Instrument: HPLC/UV; Estimated LOQ (ppm): 0.01. /From table/|A fluorescent excitation transfer immunoassay for spinosyn A, a fermentation derived insect control agent, has been developed & applied to the analysis of tap water & wastewater effluent from manufacturing plants. Fluorescein (F) & tetramethylrhodamine (TMR) were chosen as donor & quencher, respectively, for the excitation transfer. Fluorescence quenching was observed from the binding of F-labeled antigen to TMR-labeled antibody. By employing nonlabeled antigen in a competitive immunoassay format, we reversed fluorescence quenching. The assay provides a limit of detection of 0. 01 ppb & a working range of 0.05-1 ppb & allows for the rapid determination of spinosyn A in water with recovery values ranging from 96% to 120%. With the exploitation of the small size of optical fibers, fluorescence from an assay volume of 24 uL could be measured without special vessels.|Pesticide or Metabolite (M) Common Name: Spinosad; Commodity: Liver; Method Source: Dow Elanco; Method ID: GRM 95.03; Method Date: 7/21/95; Instrument: HPLC/UV; Estimated LOQ (ppm): .01. /From table/|Pesticide or Metabolite (M) Common Name: Spinosad; Commodity: Liver; Method Source: Dow Elanco; Method ID: RES95144; Method Date: 6/10/96; Instrument: Immunoassay; Estimated LOQ (ppm): 0.01. /From table/|For more Analytic Laboratory Methods (Complete) data for SPINOSYN-A (7 total), please visit the HSDB record page.

Computed Properties

Molecular Weight:732.0
XLogP3:4.9
Hydrogen Bond Acceptor Count:11
Rotatable Bond Count:9
Exact Mass:731.46084727
Monoisotopic Mass:731.46084727
Topological Polar Surface Area:111
Heavy Atom Count:52
Complexity:1290
Defined Atom Stereocenter Count:16
Undefined Atom Stereocenter Count:1
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes

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