DISCLAIMER :
THE FOLLOWING INFORMATION IS FOR INFORMATIONAL PURPOSES OR ACADEMIC STUDY
ONLY. CHECK YOUR LOCAL, STATE AND FEDERAL LAWS, AND PROCURE THE NECESSARY
PERMITS BEFORE UNDERTAKING ANY OF THE REACTIONS DESCRIBED BELOW. WIZARD
X SHALL NOT BE HELD LIABLE AND INDEMNIFIED FROM IMPEACHMENT FOR THE USE,
MISUSE, INJURY, DEATH, IMPRISIONMENT OR FELLATION DUE TO THE APPLICATION
OF THIS INFORMATION.
SYNTHESIS ROUTES.
[1] MERCAPTALS
(dithioacetals) and cyclic mercaptals, formed by reacting aldehyde with
ethanethiol, HSCH2CH2SH, and 1,2-propanedithiol, HSCH2CH2(SH)CH3 are easily
desulfurized to hydrcarbons.
J. Chem. Soc.
Perkin I,1976 pg 1886; 1978 pg 1133. J. Amer. Chem. Soc. Vol 88 pg 1828
(1966). J. Amer. Chem. Soc. Vol 66 pg 909 (1944).
[2] Pseudonitrosites
are nitrogenous compounds which are formed by the action of N2O3 (an equimolar
mixture of NO and NO2) upon etheral solutions of some unsaturated compounds,
for example propenylbenzenes. Click Here
[3] REDUCTION
with lithium aluminium hydride, LiAlH4.
[4] REDUCTION
with an excess of Raney nickel W2 and hydrogen in ethanol. MERCAPTALS (dithioacetals)
are reduced to hydrocarbons with an excess of Raney nickel W2 and refluxing
ethanol only.
J. Amer. Chem.
Soc. Vol 66 pg 909 (1944). J. Amer. Chem. Soc. Vol 70 pg 695 (1948). Org.
Reactions Vol 12 pg 356 (1962).
[5] REDUCTION
with sodium borohydride, NaBH4 + water J. Amer. Chem. Soc. Vol 71 pg 122
(1949).
[6] REDUCTION
with Alane, prepared in situ with lithium aluminium hydride, LiAlH4 + aluminium
chloride, AlCl3. Tetrahedron Lett. pg 559, 1962.
[7] PHOTOAMINATION.
Click Here
[8] DEHALOGENATION.
Converting the hydroxy group (-OH) to a -Cl, -Br or -I.
Cloro-dehalogenation
with lithium aluminium hydride.
J. Org. Chem
Vol 45 pg 849 (1982). J. Amer. Chem. Soc. Vol 95 pg 6452 (1973).
Bromo and Iodo-dehalogenation
with lithium aluminium hydride, and via catalytic reduction, or via electrochemical
dehalogenation.
Catalytic Reduction;
Chem. Ber Vol 92 pg 1700 (1959). Lithium aluminium hydride; J. Org. Chem
Vol 45 pg 849 (1982). J. Amer. Chem. Soc. Vol 95 pg 6452 (1973). Sodium
borohydride; J. Org. Chem Vol 34 pg 3923 (1969). Tetrahedron Lett. pg 3495,
1969.
[9] Direct hydroxy
group (-OH) reduction. Addition of the alcohol to dialkylcarbodiimide followed
by catalytic hydrogenation of the intermediate. Chem. Ber Vol 107 pg 1353
(1974).
[10] The alcohol
is converted to a p-toluenesulfonic ester with p-toluenesulfonic chloride
(tosyl chloride). The p-toluenesulfonic ester can be reduced via catalytic
hydrogenation as the intermediate is an alkene.
Ph-CH2-CH2-OH
+ TsCl ==>> Ph-CH2-CH2-OTs ==>> Ph-CH=CH + HOTs, or by Ph-CH2-CH2-OTs
+ NaI ==>> Ph-CH2-CH2-I + NaOTs, then reduction of Ph-CH2-CH2-I with lithium
aluminium hydride, or zinc.
Collect. Czech.
Chem. Commun. Vol 44 pg 246 (1979)
[11] REDUCTIVE
CLEAVERAGE of p-toluenesulfonylhydrazone of aldehydes to hydrocarbons.
J. Org. Chem Vol 43 pg 2299 (1978). Tetrahedron Lett. Vol 22 pg 487, 1966.
Tetrahedron Lett. Vol 19 pg 1127, 1963.
[12] Sodium borohydride
reduction; 16 moles of sodium borohydride : 1 mole of the substrate.
[13] HYDROXYLATION
OF ALKENES. Look at Vogel 5th Ed, pg 547-550. Phikal, 109 MDMA via peroxyacids.
[14] Imine formation
reactions. Many examples of this reaction, eg Phikal, 109 MDMA, Hive BB.
[15] REDUCTION
WITH Lithium aluminium hydride or Sodium borohydride. Another method is
reduction with sodium metal and ethanol. Vogel 5th Ed, pg 529. |