Deuterium-enriched aldehydes

1. A method of modulating the behavior of insects, comprising: introducing a modulating composition to an area to be protected from the insects, the modulating composition, comprising: a deuterium-enriched aldehyde pheromone of structure 1:

wherein:

there are at least 6×10 18 molecules of the aldehyde in the composition;

R x is hydrogen, wherein the deuterium isotope is present in an amount greater than 0.10% of the R x hydrogen atoms;

R 1 , R 2 and R 3 are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl;

alternatively the CR 1 R 2 R 3 moiety forms a group selected from: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl;

alternatively, CR 1 R 2 moiety forms a group selected from: an alkenyl and substituted alkenyl;

alternatively, CR 1 R 2 R 3 moiety forms a group selected from: an alkynyl and substituted alkynyl; and,

optionally, the aldehyde is substituted with C(O)R y , wherein R y is hydrogen, wherein the deuterium isotope is optionally present in an amount greater than 0.10% of the R y hydrogen atoms, provided that R x is optionally H when the deuterium isotope is present in an amount greater than 0.10% of the R y hydrogen atoms.

2. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is selected from aldehydes 2-64:

3. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is selected from aldehydes 65-358:

Ex.

Name

65.

Formaldehyde-R x

66.

2-Methyl-2-propenal-R x

67.

2-Methylpropanal-R x

68.

2-Propenal-R x

69.

2-Butenal-R x

70.

2-Methyl-2-butenal-R x

71.

2-Methylenebutanal-R x

72.

3-Methyl-2-butenal-R x

73.

3-Methyl-3-butenal-R x

74.

3-Methylbutanal-R x

75.

(E)-2-Pentenal-R x

76.

2-Methylenepentanal-R x

77.

2-Pentenal-R x

78.

3-Methyl-1-(vinyloxy)-butane-R x

79.

4-Methylpentanal-R x

80.

Furan-2-carbaldehyde-R x

81.

(E)-2-Hexenal-R x

82.

(E)-4-oxo-2-Hexenal-R x

83.

(E,E)-2,4-Dimethyl-2,4-hexadienal-R x

84.

(E,E)-2,4-Hexadienal-R x

85.

(Z)-2-Hexenal-R x

86.

(Z)-3-Hexenal-R x

87.

(Z)-4-oxo-2-Hexenal-R x

88.

1-Hexenal-R x

89.

2,3-Dihydroxybenzaldehyde-R x

90.

2-Hexenal-R x

91.

3-((E)-2-Hexenoxy)-hexanal-R x

92.

3,5-Dimethylhexanal-R x

93.

3-Ethoxyhexanal-R x

94.

3-Hydroxybenzaldehyde-R x

95.

3-Hydroxyhexanal-R x

96.

4-Hydroxy-3,5-dimethoxybenzaldehyde-R x

97.

4-Hydroxybenzaldehyde-R x

98.

5-Methylhexanal-R x

99.

Hexanal-R x

100.

(1R,2S,5S)-Iridodial-R x

101.

(1R,5S)-6,6-Dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde-R x

102.

(1S,2R,3S)-2-(1-Formylvinyl)-5-

methylcyclopentanecarbaldehyde-R x

103.

(3S,8R)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1-

carbaldehyde-R x

104.

(3S,8S)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1-

carbaldehyde-R x

105.

(5S,8S)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1-

carbaldehyde-R x

106.

(E)-2-(2-Hydroxyethyl)-6-methyl-2,5-heptadienal-R x

107.

(E)-2-(2-Hydroxyethylidene)-6-methyl-5-heptenal-R x

108.

(E)-2-Heptenal-R x

109.

(E)-2-Isopropyl-5-methyl-2-hexenal-R x

110.

(E,Z)-2,4-Heptadienal-R x

111.

(R)-2-((1R,2R,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R x

112.

(R)-2-((1S,2S,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R x

113.

(R)-2,6-Dimethyl-5-heptenal-R x

114.

(R)-7-Hydroxy-6,7-dihydro-5H-pyrrolizidine-1-carboxaldehyde-R x

115.

(S)-4-(Prop-1-en-2-yl)-cyclohex-1-enecarbaldehyde-R x

116.

(S)-7-Hydroxy-6,7-dihydro-5H-pyrrolizidine-1-carboxaldehyde-R x

117.

(Z)-2-Isopropyl-5-methyl-2-hexenal-R x

118.

1-Formyl-6,7-dihydro-5H-pyrrolizine-R x

119.

1-Formyl-7-hydroxy-6,7-dihydro-5H-pyrrolizine-R x

120.

2-(3-Methylcyclopentyl)-propanal-R x

121.

2,6-Dimethyl-5-heptenal-R x

122.

2-Acetyl-5-methylcyclopentanecarbaldehyde-R x

123.

2-Methoxybenzaldehyde-R x

124.

2-Methyl-1-cyclopentenecarboxaldehyde-R x

125.

3,3-Dimethyl-5-oxo-7-oxabicyclo[4.1.0]heptane-1-carbaldehyde-R x

126.

3-Hydroxybenzene-1,2-dicarbaldehyde-R x

127.

3-Methylbenzaldehyde-R x

128.

4-(Heptyloxy)-butanal-R x

129.

4-Methoxybenzaldehyde-R x

130.

6,7-Dihydro-5H-pyrrolizine-1-carboxaldehyde-R x

131.

6,7-Dihydro-7-oxo-5H-pyrrolizine-1-carbaldehyde-R x

132.

6-Methylheptanal-R x

133.

7-Hydroxy-6,7-dihydro-5H-pyrrolizin-1-carboxaldehyde-R x

134.

Benzaldehyde-R x

135.

Cyclohexanedial-R x

136.

Heptanal-R x

137.

Plagiodial-R x

138.

(1R,2S)-cis-2-Isopropenyl-1-methylcyclobutaneethanal-R x

139.

(1R,2S,5R,8R)-Iridodial-R x

140.

(4S)-(3-Oxoprop-1-en-2-yl)-cyclohex-1-enecarbaldehyde-R x

141.

(E)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde-R x

142.

(E)-2-(4-Methyl-3-pentenyl)-butenedial-R x

143.

(E)-2-(4-Methyl-3-pentenylidene)-butanedial-R x

144.

(E)-2,7-Octadienal-R x

145.

(E)-2-Methyl-5-(3-furyl)-2-pentenal-R x

146.

(E)-2-Octenal-R x

147.

(E)-3,7-Dimethyl-2,6-octadienal-R x

148.

(E)-3,7-Dimethyl-2,6-octadienal-R x

149.

(E)-4-oxo-2-Octenal-R x

150.

(E)-7-Methyl-2-octenal-R x

151.

(E,E)-2,4-Octadienal-R x

152.

(E,E)-2,6-Dimethyl-8-hydroxy-2,6-octadienal-R x

153.

(E,E)-2,6-Octadienal-R x

154.

(E,E)-2,6-Octadienedial-R x

155.

(E,Z)-2,4-Octadienal-R x

156.

(E,Z)-2,6-Octadienal-R x

157.

(Z)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde-R x

158.

(Z)-3,7-Dimethyl-2,6-octadienal-R x

159.

(Z,E)-3,7-Dimethyl-2,6-octadienal-R x

160.

1-Octenal-R x

161.

2-(1-Formylvinyl)-5-methylcyclopentanecarbaldehyde-R x

162.

2,6,6-Trimethyl-1-cyclohexene-1-carbaldehyde-R x

163.

2-Ethyloctanal-R x

164.

2-Hydroxy-6-methylbenzaldehyde-R x

165.

2-Methyl benzaldehyde-R x

166.

2-Octenal-R x

167.

2-Phenylpropenal-R x

168.

3,7-Dimethyl-6-octenal-R x

169.

3-Ethoxy-4-hydroxybenzaldehyde-R x

170.

3-Ethyl benzaldehyde-R x

171.

3-Isopropyl-6-methyl benzaldehyde-R x

172.

3-Octenal-R x

173.

3-oxo-4-Isopropylidene-1-cyclohexene-1-carboxyaldehyde-R x

174.

4-Hydroxy-2-methyl benzaldehyde-R x

175.

4-Hydroxy-3-methoxybenzaldehyde-R x

176.

4-Isopropenyl-1-cyclohexene-1-carbaldehyde-R x

177.

4-Isopropenyl-3-oxo-1-cyclohexene-1-carboxyaldehyde-R x

178.

4-oxo-Octenal-R x

179.

4S-4-Isopropenyl-3-oxo-1-cyclohexene-1-carboxyaldehyde-R x

180.

6,6-Dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde-R x

181.

7-Methyloctanal-R x

182.

Anisomorphal-R x

183.

cis-2-Isopropenyl-1-methylcyclobutaneethanal-R x

184.

Octanal-R x

185.

Peruphasmal-R x

186.

(E)-4,8-Nonadienal-R x

187.

(E)-8-Methyl-2-nonenal-R x

188.

(E,E)-2,4-Nonadienal-R x

189.

(E,E,E)-2,4,6-Nonatrienal-R x

190.

(E,E,Z)-2,4,6-Nonatrienal-R x

191.

(E,Z)-2,6-Nonadienal-R x

192.

(E,Z,Z)-2,4,6-Nonatrienal-R x

193.

(Z)-3-Nonenal-R x

194.

(Z)-4,8-Nonadienal-R x

195.

(Z)-4-Nonenal-R x

196.

(Z)-8-Methyl-2-nonenal-R x

197.

2-Phenyl-2-butenal-R x

198.

3-(4-Methoxyphenyl)-2-propenal-R x

199.

3-Phenyl-2-propenal-R x

200.

3-Phenylpropanal-R x

201.

6-Ethyl benzaldehyde-R x

202.

8-Methylnonanal-R x

203.

9-Acetyloxynonanal-R x

204.

Nonanal-R x

205.

(E)-2,9-Decadienal-R x

206.

(E)-2-Decenal-R x

207.

(E)-4-oxo-2-Decenal-R x

208.

(E)-8-Hydroxy-4,8-dimethyl-4,9-decadienal-R x

209.

(E)-9-Methyl-2-decenal-R x

210.

(E,E)-2,4-Decadienal-R x

211.

(E,Z)-2,4-Decadienal-R x

212.

(Z)-4-Decenal-R x

213.

(Z)-5-Decenal-R x

214.

(Z)-9-Methyl-2-decenal-R x

215.

1-Decenal-R x

216.

2-Decenal-R x

217.

2-Ethyldecanal-R x

218.

Decanal-R x

219.

(5E)-2,6,10-Trimethylundeca-5,9-dienal-R x

220.

(E)-2-Undecenal-R x

221.

(E)-6-Ethyl-2,10-dimethyl-5,9-undecadienal-R x

222.

10-Undecenal-R x

223.

2-Butyl-2-octenal-R x

224.

5-Methyl-2-phenyl-2-hexenal-R x

225.

8-Isopropyl-5-methyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-

2-carbaldehyde-R x

226.

syn-4,6-Dimethylundecanal-R x

227.

Undecanal-R x

228.

(3R,5R,9R)-3,5,9-Trimethyldodecanal-R x

229.

(3S,6E)-7-Ethyl-3,11-dimethyldodeca-6,10-dienal-R x

230.

(9R)-3,5,9-Trimethyldodecanal-R x

231.

(E)-10-Dodecenal-R x

232.

(E)-2-Dodecenal-R x

233.

(E)-3,7,11-Trimethyl-6,10-dodecadienal-R x

234.

(E)-6-Dodecenal-R x

235.

(E)-7-Dodecenal-R x

236.

(E)-8-Dodecenal-R x

237.

(E)-9,11-Dodecadienal-R x

238.

(E)-9-Dodecenal-R x

239.

(E,E)-3,7,11-Trimethyl-2,6,10-dodecatrienal-R x

240.

(E,E)-7-Ethyl-3,11-dimethyl-2,6,10-dodecatrienal-R x

241.

(E,E)-8,10-Dodecadienal-R x

242.

(E,E,E)-3,7-Dimethyl-8,11-dioxo-2,6,9-dodecatrienal-R x

243.

(E,E,Z)-3,7-Dimethyl-8,11-dioxo-2,6,9-dodecatrienal-R x

244.

(E,Z)-5,7-Dodecadienal-R x

245.

(E,Z)-7,9-Dodecadienal-R x

246.

(E,Z)-8,10-Dodecadienal-R x

247.

(S,E)-3,7,11-Trimethyl-6,10-dodecadienal-R x

248.

(Z)-2-Methyl-5-((1R,5R,6S)-2,6-dimethylbicyclo[3.1.1]hept-2-

en-6-yl)-pent-2-enal-R x

249.

(Z)-5-Dodecenal-R x

250.

(Z)-7-Dodecenal-R x

251.

(Z)-9,11-Dodecadienal-R x

252.

(Z)-9-Dodecenal-R x

253.

(Z,E)-3,7,11-Trimethyl-2,6,10-dodecatrienal-R x

254.

(Z,E)-5,7-Dodecadienal-R x

255.

(Z,E)-7-Ethyl-3,11-dimethyl-2,6,10-dodecatrienal-R x

256.

(Z,E)-8,10-Dodecadienal-R x

257.

(Z,Z)-5,7-Dodecadienal-R x

258.

2-Ethyldodecanal-R x

259.

3,7,11-Trimethyl-(E)-6,10-dodecadienal-R x

260.

Dodecanal-R x

261.

syn-4,6-Dimethyldodecanal-R x

262.

(3S,4R,6E,10Z)-3,4,7,11-Tetramethyl-6,10-tridecadienal-R x

263.

(Z)-4-Tridecenal-R x

264.

13-Acetyloxytridecanal-R x

265.

Tridecanal-R x

266.

(E)-11,13-Tetradecadienal-R x

267.

(E,E)-8,10-Tetradecadienal-R x

268.

(E,Z)-4,9-Tetradecadienal-R x

269.

(Z)-11,13-Tetradecadienal-R x

270.

(Z)-5-Tetradecenal-R x

271.

(Z)-7-Tetradecenal-R x

272.

(Z)-9,13-Tetradecadien-11-ynal-R x

273.

(Z,E)-9,12-Tetradecadienal-R x

274.

(Z,Z)-8,10-Tetradecadienal-R x

275.

(Z,Z)-9,11-Tetradecadienal-R x

276.

10,12-Tetradecadienal-R x

277.

2-Ethyltetradecanal-R x

278.

3-oxo-13-Tetradecenal-R x

279.

3-oxo-Tetradecanal-R x

280.

5,8-Tetradecadienal-R x

281.

5-Tetradecenal-R x

282.

(E)-5,9-Dimethyl-2-(6-methylhept-5-en-2-yl)-deca-4,8-dienal-R x

283.

(E,Z)-9,11-Pentadecadienal-R x

284.

(Z)-10-Pentadecenal-R x

285.

(Z)-6,14-Pentadecadienal-R x

286.

(Z,Z)-9,11-Pentadecadienal-R x

287.

2-Hexyl-2-decenal-R x

288.

Pentadecanal-R x

289.

(1R)-Pimaral-R x

290.

(E)-10-Hexadecenal-R x

291.

(E)-11-Hexadecenal-R x

292.

(E,E)-10,14-Hexadecadienal-R x

293.

(E,E)-11,13-Hexadecadienal-R x

294.

(E,E)-9,11-Hexadecadienal-R x

295.

(E,E,E)-10,12,14-Hexadecatrienal-R x

296.

(E,E,E)-3,7,11,15-tetramethyl-2,6,10,14-hexadecatetraenal-R x

297.

(E,E,Z)-10,12,14-Hexadecatrienal-R x

298.

(E,E,Z)-4,6,11-Hexadecatrienal-R x

299.

(E,E,Z,Z)-4,6,11,13-Hexadecatetraenal-R x

300.

(E,Z)-10,12-Hexadecadienal-R x

301.

(E,Z)-11,13-Hexadecadienal-R x

302.

(E,Z)-4,6-Hexadecadienal-R x

303.

(E,Z)-6,11-Hexadecadienal-R x

304.

(E,Z)-8,11-Hexadecadienal-R x

305.

(E,Z)-9,11-Hexadecadienal-R x

306.

(Z)-10-Hexadecenal-R x

307.

(Z)-12-Hexadecenal-R x

308.

(Z)-13-Hexadecen-11-ynal-R x

309.

(Z)-3-oxo-9-Hexadecenal-R x

310.

(Z,E)-10,12-Hexadecadienal-R x

311.

(Z,E)-11,13-Hexadecadienal-R x

312.

(Z,E)-7,11-Hexadecadienal-R x

313.

(Z,E)-9,11-Hexadecadienal-R x

314.

(Z,Z)-10,12-Hexadecadienal-R x

315.

(Z,Z)-11,13-Hexadecadienal-R x

316.

(Z,Z)-9,11-Hexadecadienal-R x

317.

11-Hexadecynal-R x

318.

2-Methylhexadecanal-R x

319.

7-Hexadecenal-R x

320.

9-Hexadecenal-R x

321.

(Z)-9-Heptadecenal-R x

322.

1-Heptadecenal-R x

323.

2-Heptadecenal-R x

324.

Heptadecanal-R x

325.

(E)-11-Octadecenal-R x

326.

(E)-13-Octadecenal-R x

327.

(E)-14-Octadecenal-R x

328.

(E)-2-Octadecenal-R x

329.

(E,E)-11,14-Octadecadienal-R x

330.

(E,Z)-2,13-Octadecadienal-R x

331.

(E,Z)-3,13-Octadecadienal-R x

332.

(Z)-11-Octadecenal-R x

333.

(Z)-13-Octadecenal-R x

334.

(Z)-9-Octadecenal-R x

335.

(Z,Z)-11,13-Octadecadienal-R x

336.

(Z,Z)-13,15-Octadecadienal-R x

337.

(Z,Z)-3,13-Octadecadienal-R x

338.

(Z,Z)-9,12-Octadecadienal-R x

339.

(Z,Z,Z)-9,12,15-Octadecatrienal-R x

340.

1-Octadecenal-R x

341.

9-Octadecenal-R x

342.

Octadecanal-R x

343.

(Z)-10-Nonadecenal-R x

344.

(Z)-9-Nonadecenal-R x

345.

(Z)-11-Eicosenal-R x

346.

12-Deacetoxy-12-oxo-scalaradial-R x

347.

1-Eicosenal-R x

348.

Deacetylscalaradial-R x

349.

Eicosanal-R x

350.

Scalaradial-R x

351.

Docosanal-R x

352.

Tetracosanal-R x

353.

Pentacosanal-R x

354.

Hexacosanal-R x

355.

Heptacosanal-R x

356.

Octacosanal-R x

357.

Triacontanal-R x

358.

Dotriacontanal-R x .

4. The method of claim 1 , wherein modulation, comprises: attracting an insect to a trap.

5. The method of claim 1 , wherein modulation, comprises: disrupting insect mating.

6. The method of claim 1 , wherein the deuterium isotope in R x is in an amount greater than 10 percent of the hydrogen atoms present in R x .

7. The method of claim 1 , wherein the deuterium isotope in R x is in an amount greater than 30 percent of the hydrogen atoms present in R x .

8. The method of claim 1 , wherein the deuterium isotope in R x is in an amount greater than 50 percent of the hydrogen atoms present in R x .

9. The method of claim 1 , wherein the deuterium isotope in R x is in an amount greater than 90 percent of the hydrogen atoms present in R x .

10. The method of claim 1 , wherein the method further comprises: applying the pheromone to a surface of a trap wherein the insect enters but cannot leave.

11. The method of claim 1 , wherein introducing, comprises: distributing the pheromone into the area to be protected, wherein the pheromone disrupts insect mating and is distributed impregnated on a chip, in a polymer hollow fiber, or adsorbed in a rubber septum.

12. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

13. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

14. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

15. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

16. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

17. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

18. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

19. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

20. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

21. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

22. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

23. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

24. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

25. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

26. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

27. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

28. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is:

29. The method of claim 1 , wherein the deuterium-enriched aldehyde pheromone is: