ChemWiki - User contributions [en]

It07:Azadirachtin

2007-12-01T17:58:10Z

Cpl106: /* Azadirachtin */

== Azadirachtin ==

{| class="toccolours" border="1" width="150px" style="float: right; clear: right; margin: 0 0 1em 1em; border-collapse: collapse;"
! {{chembox header}}| '''{{PAGENAME}}''' 
|-
| align="center" colspan="2" bgcolor="#ffffff" | [[Image:It07-Azadirachtin.png|300px|It07-Azadirachtin]] 
|-
| [[IUPAC nomenclature|Systematic name]]
| {{dimethyl (2aR,3S,4S,4aR,5S,7aS,8S,10R,10aS,10bR)-10-acetoxy-
3,5-dihydroxy-4-[(1aR,2S,3aS,6aS,7S,7aS)-
6a-hydroxy-7a-methyl-3a,6a,7,7a-tetrahydro-
2,7-methanofuro[2,3-b]oxireno[e]oxepin-
1a(2H)-yl]-4-methyl-8-
{[(2E)-2-methylbut-2-enoyl]oxy}octahydro-
1H-naphtho[1,8a-c:4,5-b'c']difuran-
5,10a(8H)-dicarboxylate}} 
|-
| [[Chemical formula]]
| C<sub>35</sub>H<sub>44</sub>O<sub>16</sub>
|-
| [[Molar mass]]
| 720.63 g/mol
|-
| [[Density]]
| 1.51 ± 0.1 g/cm³
|-
| [[Solubility]]
| 0.015 g/dm<sup>3</sup>
|-
| [[Boiling point]]
| 792.4 ± 60.0 °C
|-
| [[CAS registry number|CAS number]]
| 11141-17-6
|-
| [[Simplified molecular input line entry specification|SMILES]]
| <small>C\C=C(/C)\C(=O)O[C@H]1C[C@H]
([C@]2(CO[C@@H]3[C@@H]2[C@]14CO[C@@]
([C@H]4[C@]([C@@H]3O)(C)[C@@]56[C@@H]
7C[C@H]([C@@]5(O6)C)[C@]8(C=CO[C@H]8O7)O)
(C(=O)OC)O)C(=O)OC)OC(=O)C</small>
|-
| [[Hazards]]
| Possible irritant, toxicological properties have not been investigated.
|-
| {{chembox header}} | <small>[[wikipedia:Chemical infobox|Disclaimer and references]]</small>
|-
|}<noinclude>
[[Category:WikiProject Chemistry Templates|Chembox simple organic]]
</noinclude>

'''Azadirachtin''' is a triterpenoid compound extracted from the Neem tree (''Azadirachta indica''). The molecular structure is highly complex, with 16 stereogenic centers - seven of which are tetrasubstituted. Complete synthesis was first achieved by Steven Ley in 2007, 22 years after the structure was established (also by Ley and co-workers) in 1985.<ref name="synthesis">S. V. Ley, A. A. Denholm and A. Wood, Nat. Prod. Rep., 1993, 10,
109. http://www.rsc.org/ejarchive/NP/1993/NP9931000109.pdf (accessed 25 October 2007)</ref> It is a yellow-green powder, with a strong garlic-sulfur odor.<ref>Farm Chemicals Handbook. 1995. Meister Publishing Co. Willoughby, OH.</ref><ref>Thomson, W.T. Agricultural Chemicals. Book I: Insecticides. 1992. Thomson Publications, Fresno, CA.</ref>

=== Mode of Action ===
The process of moulting (shedding of exoskeleton) and metamorphosis (final transformation where insect makes transition from pupal stage to become fully adult) is triggered by prothoracicotropic hormone (PTTH) as well as ecdysone.<ref>Kimball, J. W. (9 February 2002) 'Insect Hormones', http://users.rcn.com/jkimball.ma.ultranet/BiologyPages/I/InsectHormones.html (accessed 23 October 2007)</ref> Azadirachtin blocks the action of ecdysone and hence stops moulting and subsequent growth of insects. As such, it is a good antifeedant - a substance that inhibits the insect from feeding but does not kill it directly.<ref>K. Munakata, Pure Appl. Chem., 1975, 42, 57.</ref>

=== 3d Structure ===
To zoom in/out, click on molecule and use scroll wheel on mouse.
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ATOM 1 C 0 -0.415 6.019 -1.839 0.00 0.00 C+0
ATOM 2 C 0 0.229 4.734 -2.293 0.00 0.00 C+0
ATOM 3 C 0 0.349 3.715 -1.447 0.00 0.00 C+0
ATOM 4 C 0 -0.159 3.845 -0.034 0.00 0.00 C+0
ATOM 5 C 0 0.977 2.462 -1.889 0.00 0.00 C+0
ATOM 6 O 0 1.387 2.357 -3.029 0.00 0.00 O+0
ATOM 7 O 0 1.098 1.429 -1.032 0.00 0.00 O+0
ATOM 8 C 0 1.715 0.199 -1.467 0.00 0.00 C+0
ATOM 9 C 0 3.222 0.270 -1.199 0.00 0.00 C+0
ATOM 10 C 0 3.406 0.496 0.303 0.00 0.00 C+0
ATOM 11 C 0 2.893 -0.685 1.082 0.00 0.00 C+0
ATOM 12 C 0 2.537 -0.280 2.535 0.00 0.00 C+0
ATOM 13 O 0 1.085 -0.249 2.561 0.00 0.00 O+0
ATOM 14 C 0 0.707 -1.383 1.759 0.00 0.00 C+0
ATOM 15 C 0 1.631 -1.350 0.562 0.00 0.00 C+0
ATOM 16 C 0 1.123 -1.036 -0.789 0.00 0.00 C+0
ATOM 17 C 0 1.530 -2.235 -1.720 0.00 0.00 C+0
ATOM 18 O 0 0.437 -3.158 -1.560 0.00 0.00 O+0
ATOM 19 C 0 -0.757 -2.339 -1.642 0.00 0.00 C+0
ATOM 20 C 0 -0.408 -1.020 -0.954 0.00 0.00 C+0
ATOM 21 C 0 -1.181 -0.668 0.283 0.00 0.00 C+0
ATOM 22 C 0 -0.762 -1.503 1.489 0.00 0.00 C+0
ATOM 23 O 0 -1.114 -2.873 1.319 0.00 0.00 O+0
ATOM 24 C 0 -0.965 0.818 0.643 0.00 0.00 C+0
ATOM 25 C 0 -2.688 -0.808 0.062 0.00 0.00 C+0
ATOM 26 C 0 -3.420 0.335 -0.683 0.00 0.00 C+0
ATOM 27 C 0 -4.914 0.008 -0.432 0.00 0.00 C+0
ATOM 28 C 0 -4.907 -0.407 1.077 0.00 0.00 C+0
ATOM 29 C 0 -3.641 -1.295 1.169 0.00 0.00 C+0
ATOM 30 O 0 -3.285 -2.108 0.017 0.00 0.00 O+0
ATOM 31 C 0 -3.133 -1.665 2.564 0.00 0.00 C+0
ATOM 32 C 0 -4.574 0.908 1.789 0.00 0.00 C+0
ATOM 33 C 0 -4.371 0.829 3.277 0.00 0.00 C+0
ATOM 34 C 0 -3.294 1.573 3.533 0.00 0.00 C+0
ATOM 35 O 0 -2.752 2.121 2.393 0.00 0.00 O+0
ATOM 36 C 0 -3.106 1.218 1.360 0.00 0.00 C+0
ATOM 37 O 0 -3.088 1.564 0.007 0.00 0.00 O+0
ATOM 38 O 0 -5.486 1.948 1.431 0.00 0.00 O+0
ATOM 39 C 0 -1.074 -2.085 -3.100 0.00 0.00 C+0
ATOM 40 O 0 -0.407 -2.604 -3.963 0.00 0.00 O+0
ATOM 41 O 0 -2.098 -1.283 -3.434 0.00 0.00 O+0
ATOM 42 C 0 -2.472 -1.126 -4.828 0.00 0.00 C+0
ATOM 43 O 0 -1.827 -3.065 -1.054 0.00 0.00 O+0
ATOM 44 C 0 3.984 -1.724 1.149 0.00 0.00 C+0
ATOM 45 O 0 3.794 -2.829 0.699 0.00 0.00 O+0
ATOM 46 O 0 5.165 -1.421 1.710 0.00 0.00 O+0
ATOM 47 C 0 6.216 -2.422 1.775 0.00 0.00 C+0
ATOM 48 O 0 4.819 0.678 0.587 0.00 0.00 O+0
ATOM 49 C 0 5.356 1.908 0.560 0.00 0.00 C+0
ATOM 50 O 0 4.664 2.864 0.299 0.00 0.00 O+0
ATOM 51 C 0 6.822 2.097 0.855 0.00 0.00 C+0
ATOM 52 H 0 -0.423 6.732 -2.663 0.00 0.00 H+0
ATOM 53 H 0 -1.438 5.820 -1.521 0.00 0.00 H+0
ATOM 54 H 0 0.151 6.434 -1.005 0.00 0.00 H+0
ATOM 55 H 0 0.594 4.641 -3.306 0.00 0.00 H+0
ATOM 56 H 0 -0.589 4.836 0.108 0.00 0.00 H+0
ATOM 57 H 0 -0.923 3.089 0.149 0.00 0.00 H+0
ATOM 58 H 0 0.666 3.703 0.664 0.00 0.00 H+0
ATOM 59 H 0 1.568 0.100 -2.552 0.00 0.00 H+0
ATOM 60 H 0 3.701 -0.658 -1.507 0.00 0.00 H+0
ATOM 61 H 0 3.653 1.107 -1.753 0.00 0.00 H+0
ATOM 62 H 0 2.864 1.390 0.605 0.00 0.00 H+0
ATOM 63 H 0 2.907 -1.026 3.235 0.00 0.00 H+0
ATOM 64 H 0 2.941 0.703 2.768 0.00 0.00 H+0
ATOM 65 H 0 0.991 -2.265 2.340 0.00 0.00 H+0
ATOM 66 H 0 1.941 -2.394 0.482 0.00 0.00 H+0
ATOM 67 H 0 1.631 -1.901 -2.750 0.00 0.00 H+0
ATOM 68 H 0 2.467 -2.676 -1.376 0.00 0.00 H+0
ATOM 69 H 0 -0.627 -0.221 -1.697 0.00 0.00 H+0
ATOM 70 H 0 -1.302 -1.121 2.371 0.00 0.00 H+0
ATOM 71 H 0 -0.821 -3.337 2.115 0.00 0.00 H+0
ATOM 72 H 0 -1.507 1.446 -0.064 0.00 0.00 H+0
ATOM 73 H 0 -1.333 1.005 1.652 0.00 0.00 H+0
ATOM 74 H 0 0.099 1.052 0.596 0.00 0.00 H+0
ATOM 75 H 0 -3.174 0.367 -1.745 0.00 0.00 H+0
ATOM 76 H 0 -5.537 0.888 -0.590 0.00 0.00 H+0
ATOM 77 H 0 -5.243 -0.818 -1.062 0.00 0.00 H+0
ATOM 78 H 0 -5.822 -0.893 1.418 0.00 0.00 H+0
ATOM 79 H 0 -3.972 -1.977 3.185 0.00 0.00 H+0
ATOM 80 H 0 -2.416 -2.482 2.485 0.00 0.00 H+0
ATOM 81 H 0 -2.649 -0.799 3.016 0.00 0.00 H+0
ATOM 82 H 0 -4.972 0.284 3.990 0.00 0.00 H+0
ATOM 83 H 0 -2.892 1.728 4.524 0.00 0.00 H+0
ATOM 84 H 0 -2.519 0.307 1.483 0.00 0.00 H+0
ATOM 85 H 0 -5.165 2.758 1.853 0.00 0.00 H+0
ATOM 86 H 0 -2.835 -2.078 -5.216 0.00 0.00 H+0
ATOM 87 H 0 -3.259 -0.377 -4.911 0.00 0.00 H+0
ATOM 88 H 0 -1.603 -0.807 -5.404 0.00 0.00 H+0
ATOM 89 H 0 -1.886 -3.908 -1.525 0.00 0.00 H+0
ATOM 90 H 0 7.094 -1.996 2.260 0.00 0.00 H+0
ATOM 91 H 0 5.865 -3.280 2.347 0.00 0.00 H+0
ATOM 92 H 0 6.477 -2.741 0.766 0.00 0.00 H+0
ATOM 93 H 0 7.391 2.026 -0.072 0.00 0.00 H+0
ATOM 94 H 0 6.979 3.078 1.303 0.00 0.00 H+0
ATOM 95 H 0 7.156 1.323 1.546 0.00 0.00 H+0
CONECT 1 2 52 53 54 NONE 100
CONECT 2 1 3 55 0 NONE 101
CONECT 3 2 4 5 0 NONE 102
CONECT 4 3 56 57 58 NONE 103
CONECT 5 3 6 7 0 NONE 104
CONECT 6 5 0 0 0 NONE 105
CONECT 7 5 8 0 0 NONE 106
CONECT 8 7 16 9 59 NONE 107
CONECT 9 8 10 60 61 NONE 108
CONECT 10 9 11 48 62 NONE 109
CONECT 11 10 15 12 44 NONE 110
CONECT 12 11 13 63 64 NONE 111
CONECT 13 12 14 0 0 NONE 112
CONECT 14 13 22 15 65 NONE 113
CONECT 15 14 11 16 66 NONE 114
CONECT 16 15 8 20 17 NONE 115
CONECT 17 16 18 67 68 NONE 116
CONECT 18 17 19 0 0 NONE 117
CONECT 19 18 20 39 43 NONE 118
CONECT 20 19 16 21 69 NONE 119
CONECT 21 20 22 24 25 NONE 120
CONECT 22 21 14 23 70 NONE 121
CONECT 23 22 71 0 0 NONE 122
CONECT 24 21 72 73 74 NONE 123
CONECT 25 21 29 30 26 NONE 124
CONECT 26 25 37 27 75 NONE 125
CONECT 27 26 28 76 77 NONE 126
CONECT 28 27 29 32 78 NONE 127
CONECT 29 28 25 30 31 NONE 128
CONECT 30 29 25 0 0 NONE 129
CONECT 31 29 79 80 81 NONE 130
CONECT 32 28 36 33 38 NONE 131
CONECT 33 32 34 82 0 NONE 132
CONECT 34 33 35 83 0 NONE 133
CONECT 35 34 36 0 0 NONE 134
CONECT 36 35 32 37 84 NONE 135
CONECT 37 36 26 0 0 NONE 136
CONECT 38 32 85 0 0 NONE 137
CONECT 39 19 40 41 0 NONE 138
CONECT 40 39 0 0 0 NONE 139
CONECT 41 39 42 0 0 NONE 140
CONECT 42 41 86 87 88 NONE 141
CONECT 43 19 89 0 0 NONE 142
CONECT 44 11 45 46 0 NONE 143
CONECT 45 44 0 0 0 NONE 144
CONECT 46 44 47 0 0 NONE 145
CONECT 47 46 90 91 92 NONE 146
CONECT 48 10 49 0 0 NONE 147
CONECT 49 48 50 51 0 NONE 148
CONECT 50 49 0 0 0 NONE 149
CONECT 51 49 93 94 95 NONE 150
END NONE 151
70
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=== Sources and Synthesis ===
The Azadirachtin molecule has a complex molecular structure which is mainly the reason why it has taken so long for a successful synthesis path to be found. There are 16 continuous stereogenic centres, seven of which are tetrasubstituted carbons. It is sensitive to both acid and base and is unstable in light. The C8-C14 bond is of particular importance as it was the hardest bond to create given the highly hindered environment around it. There are also intra-molecular hydrogen-bonds which impose even more conformational considerations when considering a synthetic path.

[[Image:C18-c14.jpg]]

The synthetic path can be summarised as the fusing of a pyran and decalin fragment by selective O-coupling. The crucial C8-C14 bond is then formed under thermal or gold(I)-catalysed conditions via a Claisen rearrangement. The tricyclic system is then formed by a radical cyclization. The final step involves a selective epoxidation. This was also a challenge to the acheive synthetically, but on prolonged heating with magnesium monoperoxyphthalate in the presence of a radical inhibitor, complete synthesis of Azadirachtin was achieved.

Azadirachtin can also be easily extracted from the seeds of the Neem tree. A polar solvent such as water, ethanol or methanol will suffice. In fact, Indian villagers have been known to crush the seeds and soak them in cold water. After soaking overnight, the emulsion at the top is applied directly to plants.

The exact biosynthesis of Azadirachtin is unknown but most certainly proceeds via a steroid modification.
<ref>Synthesis of Azadirachtin: A Long but Successful Journey Gemma E. Veitch, Edith Beckmann, Brenda J. Burke, Alistair Boyer, Sarah L. Maslen, and
Steven V. Ley</ref>

==References==
<references/>

2007-10-22T13:54:03Z

Cpl106: /* '''Azadirachtin''' */

It:projects

2007-10-22T13:53:45Z

Cpl106: /* Supplemental Project Page */

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