15-[5-(Dimethylamino)-6-methyloxan-2-yl]oxy-19-ethyl-14-methyl-7-(3,4,5-trimethoxy-6-methyloxan-2-yl)oxy-20-oxatetracyclo[10.10.0.02,10.05,9]docosa-3,11-diene-13,21-dione

Base Information

• Chemical Name: 15-[5-(Dimethylamino)-6-methyloxan-2-yl]oxy-19-ethyl-14-methyl-7-(3,4,5-trimethoxy-6-methyloxan-2-yl)oxy-20-oxatetracyclo[10.10.0.02,10.05,9]docosa-3,11-diene-13,21-dione
• CAS No.: 131929-60-7
• Molecular Formula: C41H65NO10
• Molecular Weight: 731.968
• Hs Code.: 2932209090
• European Community (EC) Number: 620-162-1
• DSSTox Substance ID: DTXSID00861315
• Mol file: 131929-60-7.mol

Synonyms:131929-60-7;DTXSID00861315;FT-0696856;FT-0701197;13-{[5-(Dimethylamino)-6-methyloxan-2-yl]oxy}-9-ethyl-14-methyl-7,15-dioxo-2,3,3a,5a,5b,6,7,9,10,11,12,13,14,15,16a,16b-hexadecahydro-1H-as-indaceno[3,2-d]oxacyclododecin-2-yl 6-deoxy-2,3,4-tri-O-methylhexopyranoside

Chemical Property of 15-[5-(Dimethylamino)-6-methyloxan-2-yl]oxy-19-ethyl-14-methyl-7-(3,4,5-trimethoxy-6-methyloxan-2-yl)oxy-20-oxatetracyclo[10.10.0.02,10.05,9]docosa-3,11-diene-13,21-dione

Chemical Property:

• Vapor Pressure: 0mmHg at 25°C
• Melting Point: 84oC to 99.5oC
• Refractive Index: 1.54
• Boiling Point: 801.515 °C at 760 mmHg
• PKA: Spinosyn A: 8.1 (base); Spinosyn D: 7.8 (base)
• Flash Point: 438.541 °C
• PSA: 111.22000
• Density: 1.167 g/cm³
• LogP: 5.48740
• Solubility.: Soluble in DMSO
• Water Solubility.: Spinosyn A: 290 mg l-1 (pH 5); Spinosyn D: 29 mg l-1 (pH 5)
• XLogP3: 4.9
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 11
• Rotatable Bond Count: 9
• Exact Mass: 731.46084727
• Heavy Atom Count: 52
• Complexity: 1290

Purity/Quality:

99% ^*data from raw suppliers

SpinosynA ^*data from reagent suppliers

Safty Information:

• Pictogram(s):  
• Hazard Codes: 

MSDS Files:

SDS file from LookChem

Useful:

• Chemical Classes: Pesticides -> Other Insecticides
• Canonical SMILES: CCC1CCCC(C(C(=O)C2=CC3C4CC(CC4C=CC3C2CC(=O)O1)OC5C(C(C(C(O5)C)OC)OC)OC)C)OC6CCC(C(O6)C)N(C)C
• 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.

Technology Process of 15-[5-(Dimethylamino)-6-methyloxan-2-yl]oxy-19-ethyl-14-methyl-7-(3,4,5-trimethoxy-6-methyloxan-2-yl)oxy-20-oxatetracyclo[10.10.0.02,10.05,9]docosa-3,11-diene-13,21-dione

There total 50 articles about 15-[5-(Dimethylamino)-6-methyloxan-2-yl]oxy-19-ethyl-14-methyl-7-(3,4,5-trimethoxy-6-methyloxan-2-yl)oxy-20-oxatetracyclo[10.10.0.02,10.05,9]docosa-3,11-diene-13,21-dione which guide to synthetic route it. The literature collected by LookChem mainly comes from the sharing of users and the free literature resources found by Internet computing technology. We keep the original model of the professional version of literature to make it easier and faster for users to retrieve and use. At the same time, we analyze and calculate the most feasible synthesis route with the highest yield for your reference as below:

synthetic route:

Reference yield:

methyl 4-formylbutanoate (6026-86-4) → spinosyn A (131929-60-7)

Guidance literature:

Multi-step reaction with 16 steps

1: (-)-(1S,2R)-N,N-dibutylnorephedrine / hexane; toluene / 72 h / 0 °C

2: 84 percent / 2,6-lutidine / CH₂Cl₂ / 2 h / Ambient temperature

3: 94 percent / DIBAL-H / CH₂Cl₂; toluene / 0.5 h / -78 °C

4: 1.) Bu₂BOTf, Et₃N / 1.) CH₂Cl₂, from 0 to 5 deg C, 20 min, 2.) CH₂Cl₂, from -78 to 0 deg C, 3 h

5: 1.41 g / DMAP / CH₂Cl₂ / 144 h / Ambient temperature

6: 30percent aq. H₂O₂, LiOH / H₂O; tetrahydrofuran; dimethylformamide / 0 °C

7: oxalyl chloride / dimethylformamide; hexane / 0.75 h / Ambient temperature

8: 1.) Me₃SnSnMe₃, (Ph₃P)4Pd, LiCl, 2.) Pd₂(dba)3*CHCl₃, (i-Pr)2NEt / 1.) THF, 60 deg C, 2 d, 2.) benzene, RT, 6 h

9: DDQ, phosphate buffer / CH₂Cl₂ / 2 h / 0 °C

10: Jones reagent / acetone / 1.5 h / 0 °C

11: aq. AcOH / tetrahydrofuran / 24 h / 0 - 20 °C

12: 2,4,6-trichlorobenzoyl chlorie, DMAP, Et₃N / benzene

13: 63 percent / methanolic K₂CO₃ / 48 h / Heating

14: 85 percent / trityl perchlorate / toluene / 3.17 h / 0 - 20 °C

15: 91 percent / 49percent aq. HF / acetonitrile / 24 h

16: AgOTf₃ / CH₂Cl₂ / 3 h

With 2,6-dimethylpyridine; dmap; tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; lithium hydroxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾; jones reagent; phosphate buffer; oxalyl dichloride; di-n-butylboryl trifluoromethanesulfonate; 2,4,6-trichlorobenzoyl chloride; hydrogen fluoride; dihydrogen peroxide; silver trifluoromethanesulfonate; hexamethyldistannane; triphenylmethyl perchlorate; diisobutylaluminium hydride; potassium carbonate; (1S,2R)-(-)-2-(N,N-di-n-butylamino)-1-phenylpropan-1-ol; acetic acid; triethylamine; N-ethyl-N,N-diisopropylamine; 2,3-dicyano-5,6-dichloro-p-benzoquinone; lithium chloride; In tetrahydrofuran; hexane; dichloromethane; water; N,N-dimethyl-formamide; acetone; toluene; acetonitrile; benzene;

DOI:10.1021/ja974010k

Reference yield:

D-forosamine (56587-30-5) → spinosyn A (131929-60-7)

Guidance literature:

Multi-step reaction with 2 steps

1: 1.) diethyl azodicarboxylate, PPh₃ / 1.) THF, -50 deg C, 10 min, 2.) THF, from -50 to 20 deg C, 3 h

2: AgOTf₃ / CH₂Cl₂ / 3 h

With silver trifluoromethanesulfonate; triphenylphosphine; diethylazodicarboxylate; In dichloromethane;

DOI:10.1021/ja974010k

Reference yield:

(S)-5-Hydroxy-heptanoic acid methyl ester (118545-01-0) → spinosyn A (131929-60-7)

Guidance literature:

Multi-step reaction with 15 steps

1: 84 percent / 2,6-lutidine / CH₂Cl₂ / 2 h / Ambient temperature

2: 94 percent / DIBAL-H / CH₂Cl₂; toluene / 0.5 h / -78 °C

3: 1.) Bu₂BOTf, Et₃N / 1.) CH₂Cl₂, from 0 to 5 deg C, 20 min, 2.) CH₂Cl₂, from -78 to 0 deg C, 3 h

4: 1.41 g / DMAP / CH₂Cl₂ / 144 h / Ambient temperature

5: 30percent aq. H₂O₂, LiOH / H₂O; tetrahydrofuran; dimethylformamide / 0 °C

6: oxalyl chloride / dimethylformamide; hexane / 0.75 h / Ambient temperature

7: 1.) Me₃SnSnMe₃, (Ph₃P)4Pd, LiCl, 2.) Pd₂(dba)3*CHCl₃, (i-Pr)2NEt / 1.) THF, 60 deg C, 2 d, 2.) benzene, RT, 6 h

8: DDQ, phosphate buffer / CH₂Cl₂ / 2 h / 0 °C

9: Jones reagent / acetone / 1.5 h / 0 °C

10: aq. AcOH / tetrahydrofuran / 24 h / 0 - 20 °C

11: 2,4,6-trichlorobenzoyl chlorie, DMAP, Et₃N / benzene

12: 63 percent / methanolic K₂CO₃ / 48 h / Heating

13: 85 percent / trityl perchlorate / toluene / 3.17 h / 0 - 20 °C

14: 91 percent / 49percent aq. HF / acetonitrile / 24 h

15: AgOTf₃ / CH₂Cl₂ / 3 h

With 2,6-dimethylpyridine; dmap; tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; lithium hydroxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾; jones reagent; phosphate buffer; oxalyl dichloride; di-n-butylboryl trifluoromethanesulfonate; 2,4,6-trichlorobenzoyl chloride; hydrogen fluoride; dihydrogen peroxide; silver trifluoromethanesulfonate; hexamethyldistannane; triphenylmethyl perchlorate; diisobutylaluminium hydride; potassium carbonate; acetic acid; triethylamine; N-ethyl-N,N-diisopropylamine; 2,3-dicyano-5,6-dichloro-p-benzoquinone; lithium chloride; In tetrahydrofuran; hexane; dichloromethane; water; N,N-dimethyl-formamide; acetone; toluene; acetonitrile; benzene;

DOI:10.1021/ja974010k

upstream raw materials:

(2R,3aS,5aR,5bS,9S,13S,14R,16aS,16bR)-9-ethyl-13-hydroxy-14-methyl-2-(((2R,3R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydro-2H-pyran-2-yl)oxy)-3,3a,5b,6,9,10,11,12,13,14,16a,16b-dodecahydro-1H-as-indaceno[3,2-d][1]oxacyclododecine-7,15(2H,5aH)-dione

methyl 4-formylbutanoate

D-forosamine

(S)-5-Hydroxy-heptanoic acid methyl ester

Refernces

• 1、 Paquette, Leo A.,Collado, Iván,Purdie, Mark. "Total synthesis of spinosyn A. 2. Degradation studies involving the pure factor and its complete reconstitution". . p. 2553 - 2562. Retrieved 2007/10/03.