P2P [Phenylacetone] via aldol & Baeyer/Villiger

Guest · Thu Apr 07, 2005 11:16 am

Vaulable chemistry- thankyou

We all are very honoured to have such chemists like IndoleAmine, Bio, and Twodogs contribute to this very exciting synthesis,

I have follwed it very closely, and can comment on a few things that i have noticed doing this type of reaction

So just a quick thankyou to all three of you for this cutting edge synthesis,
I saw this synth coming a few years ago, And i saw the simple power to its beauty,

I am extremely glad to see the further progress, and am just very proud that our members, can learn so much from these our members, in this particular route

Well done, and I will make sure that members from years to come, will have access to this information

syn

THOTH · Thu Jun 09, 2005 10:07 pm

A Wile E steroid is PLUReality. McKenna, although somewhat soothed by the DUMB ass white boy y a THOTHache and the rott about a gynocologist, still cooks mth for her from the head, seek her a rott with the woMAN, and getes the big picture the DARK side of her recepter.

If the homeos divines some rott, then the biker inside another genetic transformaer get a bigger hard drive for my rants!.

Some aldol refs: =)

Reactants:
benzaldehyde
butan-2-one

Products:
3-methyl-4-phenyl-but-3-en-2-one
2-methyl-1,5-diphenyl-penta-1,4-dien-3-one

Reagent:
aqueous HCl

Journal:
Metayer; Epinay; C. R. Hebd. Seances Acad. Sci.; 226; 1948; 1095.

---------

Reactant:
butan-2-one
benzaldehyde

Product:
3-methyl-4-phenyl-but-3-en-2-one

Yield: 80 percent
Reagent: HCl
Ref: Padmavathi, V.; Reddy, T. V. Ramana; Reddy, K. Venugopal; Reddy, K. Audisesha; Reddy, D. Bhaskar; Indian J. Chem. Sect. B; EN; 40; 8; 2001; 667 - 673.

Yield: 85 percent
Reagent: H2SO4, AcOH
Time: 20 hour(s)
Other Conditions: Ambient temperature
Ref: Kawai, Yasushi; Saitou, Kentarou; Hida, Kouichi; Dao, Duc Hai; Ohno, Atsuyoshi; Bull. Chem. Soc. Jpn.; EN; 69; 9; 1996; 2633-2638.

Reagent: H2SO4, AcOH
Ref: Kawai, Yasushi; Saitou, Kentarou; Hida, Kouichi; Ohno, Atsuyoshi; Tetrahedron: Asymmetry; EN; 6; 9; 1995; 2143-2144.

Reagent: HCl
Ref. 1: Zielinski,W.; Pol. J. Chem.; EN; 52; 1978; 2233-2241.
Ref. 2: Goszczynski,S. et al.; Pol. J. Chem.; EN; 53; 1979; 849-853.

Reagent: HBr
Ref: Massara; ; Gazz. Chim. Ital.; 67; 1937; 440, 442.

Reagent: sulfuric acid
Ref.: Gheorghiu; Arwentiew; Bull. Soc. Chim. Fr.; <4>47; 1930; 195,199,200;
Ann. Sci. Univ. Jassy,Sect. 1; 16; 1931; 536,540,542.

Reagent: HCl
Ref. 1 : Gettler; Hammett; J. Am. Chem. Soc.; 65; 1943; 1824, 1825.
Ref. 2 : Massara; Gazz. Chim. Ital.; 63; 1933; 199, 202.

-------------

Reactant:
butan-2-one
benzaldehyde

Product:
3-methyl-4-phenyl-but-3-en-2-one

Reagent: hydrogen chloride
Ref: Harries; Mueller; Chem. Ber.; 35; 1902; 970.

Reagent: aq. HCl
Ref: McGreer,D.E.; McKinley,J.W.; Can. J. Chem.; EN; 49; 1971; 105-117.

Reagent: HCl
Ref. 1: Otto,H.-H.; Ebner,U.; Arch.Pharm.(Weinheim Ger.); GE; 309; 1976; 969-978.
Ref. 2: Appriou,P. et al.; Bull. Soc. Chim. Fr.; FR; 1970; 1497-1502.
Ref. 3: Kotlyarevskii,I.L. et al.; Bull.Acad.Sci.USSR Div.Chem.Sci.(Engl.Transl.); EN; 5; 1966; 867-871;
Izv. Akad. Nauk SSSR Ser. Khim.; RU; 5; 1966; 909-914.
Ref. 4: Dimmock,J.R.; Taylor,W.G.; J. Pharm. Sci.; EN; 64; 1975; 241-248.

Yield: 90 percent
Catalyst: RuCl3
Time: 16 hour(s)
Temperature: 120 C
Other Conditions: Heating
Ref: Iranpoor, Nasser; Kazemi, Foad; Tetrahedron; EN; 54; 32; 1998; 9475 - 9480.

--------------

Reactant:
butan-2-one
benzaldehyde

Product:
2-methyl-1.5-diphenyl-pentadien-(1.4)-one-(3)
3-methyl-4-phenyl-but-3-en-2-one

Reagent: concentrated aqueous hydrochloric acid
Ref. 1: Metayer; Epinay; C. R. Hebd. Seances Acad. Sci.; 226; 1948; 1095.
Ref. 2: Metayer; Ann.Chim.(Paris); <12>4; 1949; 242;
C. R. Hebd. Seances Acad. Sci.; 226; 1948; 500.

The rott form a biker thoroughly fuckes a BUBBLE about a prOn, or an US military hardly makes love to a butandiol. He called her TOMATRIX (or was it THOTHLUNA?).

bio · Working Bee

Good grief; I haven't a clue what you're trying to say but thanks anyway for the refs.

JACS 54, 336 is the method preferred after trying a few others all using HCl dry gas. The yield is about 90% or a little more sometimes.

But this ref caught my eye as it could be the answer to the tedious gassing for hours and stirring in the ice bath for 16-18hrs.

See this one Java??

Those damn japanese again and I thought the Boeseken articles in French were hard! Who knows it's recent enough that it probably has some english sprinkled though it.

Yield: 85 percent
Reagent: H2SO4, AcOH
Time: 20 hour(s)
Other Conditions: Ambient temperature
Ref: Kawai, Yasushi; Saitou, Kentarou; Hida, Kouichi; Dao, Duc Hai; Ohno, Atsuyoshi; Bull. Chem. Soc. Jpn.; EN; 69; 9; 1996; 2633-2638.

Reagent: H2SO4, AcOH
Ref: Kawai, Yasushi; Saitou, Kentarou; Hida, Kouichi; Ohno, Atsuyoshi; Tetrahedron: Asymmetry; EN; 6; 9; 1995; 2143-2144.

FRED · Tue Oct 04, 2005 3:11 am

ive been reading this fictional synthesis and i havent seen anything about mek having 2 alpha hydrogens thus giving 2 products and also its my understanding that benzaldehyde has no apha hydrogens and doesnt self condense contrary to what some else mentioned. seems 50 percent would be the theoreticall quantitive yield.

the enol formed by mek can have its double bond one way or the other i see no reson why it would favor the ethyl side or the methyl side any carbon next to a double bonded oxygen to a carbon is an alpha carbon hence its hydrogens are alpha carbons am i missing something or does the beta carbon have something to do with these?

but according to solomons i believe i am correct.

from what ive read looks like benzene and chloro acetone seems easy if one had benzene does anyone have any ideas for toluene to benzene? benzene seems hard to get also sodium borohydride is getting hard to get, any thoughts on adams catalyst?

bio · Working Bee

Since you seem to know all about it then don't waste your time performing this "fictional synthesis".

Benzene is no more difficult to purchase than PhMe from a chemical supplier. In recent years the price has skyrocketed but the availability remains about the same.