Author Topic: New method for P2P  (Read 5703 times)

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twodogs

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New method for P2P
« on: December 09, 2001, 03:01:00 PM »
The following reactions are part of this novel synthesis of P2P:

1) An acid catalysed Aldol condensation of Benzaldehyde and Methyl Ethyl Ketone to give Methyl Phenyl Butenone:

C6H5CHO + CH3CH2COCH3 + HCl(g) ---> C6H5CH=C(COCH3)CH3

2) The unsaturated ketone undergoes the Baeyer-Villiger oxidation with peroxy acids to give the enol ester of Phenyl propanone:

C6H5CH=C(COCH3)CH3 + RCO3H ----> C6H5CH=C(OCOCH3)CH3

3) The enol ester is then saponified with 10% NaOH solution to give Phenyl Propanone in about 35% yield based on the unsaturated ketone.


The Aldol Condensation.

The directions for this are in Organic Reactions

200 gms of Benzaldehyde and 300 gms of Methyl Ethyl Ketone are mixed in a 1 litre beaker and cooled below 5°C. HCl gas is bubbled through until 40gms has been added. The mixture goes from a clear solution to a red colour and becomes turbid so that you can't see through it. The mixture is kept over night and becomes a brown colour. It is washed with water and then 10% NaOH solution, the organic layer seperated and distilled. At 240°C a yellow oil comes accross and the temperature gradually rises to 260°C.

The oil can be crystalized by cooling in the freezer overnight. This in itself does not induce crystalization but if you also put a spoon in the freezer and then dip it in and out of the cool mixture you get some seed crystals that induce crystalization. The mass turns from an orange oil to sulfur coloured crystals, mp 38°C, 180 gms (Methyl Phenyl Butenone)


The Baeyer-Villiger Oxidation

The reaction of the above unsaturated ketone with peracetic acid was first done by Boesken reported in Rec. Trav. Chim.  55, 786 (1936). There is some discussion of this also in

Patent US3980708

.  Also see Organic Reactions Vols 9 & 43 I  think.  By following the directions in

Patent US5670661

you will get about 35% ketone based on the weight of the unsaturated ketone used. In that patent it is suggested that by recycling a higher percentage can be achieved.

To a 1 litre flask is added 625 ml of Glacial acetic acid and 143 grms of Sodium Perborate. To this is added 100 grms of the methyl phenyl butenone with stirring and the mixture is heated to 50°C. The mixture will heat up so  care has to be taken ie cooling. However if the mix gets too cool it solidifies. Stirring and heating continued for about 6 hours. Cooled poured into 1 litre H2O and extracted with toluene or DCM. The solvent is distilled leaving a yellow oil that has a pleasant smell. This is added to 500 mls of 10% NaOH solution (50/50 H20:EtOH) and stirred for 1-2 hours extracted with toluene or DCM and distilled and the fraction boiling between 210-220°C collected Phenyl-2-Propanone (About 35 gms)

In the Organic Reactions review of the Baeyer-Villiger there is a reference to the oxidation of alpha Methyl Cinnamaldehyde using H2O2 catalysed by a nitrobenzene selenic acid or something like that to give the same enol ester as above but in 90% yield.

foxy2

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Re: New method for P2P
« Reply #1 on: December 09, 2001, 04:57:00 PM »
Here are some references for the first reaction
The product is this correct?
3-methyl-4-phenyl-3-Buten-2-one

Preparation of 3-methyl-3-penten-2-one and its analogs.
Pishch. Prom-st. (Moscow)  (1990),   (10),  44-5.
Journal  written in Russian. 
Abstract
MeCOEt condensed with RCHO (R = Me, Et, Pr, Me2CH, MeOC6H4, PhCH:CH, Ph) in the presence of H2SO4 at 60-65° to give 40-79% RCH:CMeCOMe.  Analogous reaction of R1CH2COR2 [R1R2 = (CH2)3, (CH2)10; R1 = H, R2 = Ph, CH2CHMe2; R1 = C5H11, R2 = Me] with MeCHO (from paraldehyde) gave 8.6-38% MeCH:CR1COR2. 


Aldol condensation of butanone with various aldehydes.    
Sasaki, Kazuhiro.    Kobayashi Perfum. Co.,  Ichikawa,  Japan.   
Nippon Kagaku Zasshi  (1968),  89(8),  797-804. 
Journal  written in Japanese.   
Abstract
Condensation of MeCOEt (I) with various aldehydes was investigated to find the effect of conditions on the ratio of RCH:CHCOEt (II) and RCH:CMeAc (III).  Citral and I, in the presence of alkali hydroxide or NaOEt, gave products contg. >86.8% II, whereas MeOH-KOH yielded products contg. III as a main product.  Citronella (IV) and I gave similar results except that Me2C:CHCH2CH2CHMeCH2CH(OMe)CH2COEt was formed using MeOH-KOH and Me2C:CHCH2CH2CH(Me)CH2CH(OH)CHMeAc was obtained with EtONa.  The results indicate that aldol corresponding to II is more readily dehydrated than that corresponding to III.  Condensation of IV with Me2CO in the presence of MeOH-KOH gave a mixt. of Me2C:CHCH2CH2CHMeCH2CH:CHAc and Me2C:CHCH2CH2CHMeCH2CH(OMe)CH2Ac.  Similar reaction of I with Et2CO gave Me2C:-CHCH2CH2CHMeCH2CH:CMeCOEt, b0.55 101-7°.  Condensation of I with BzH, PhCH:CHCHO (V) and furfural (VI) showed that the ratio II-III is also dependent on the type of aldehyde.  III is favored when KOH-MeOH is used with BzH and V, compared with the results with aq. NaOH, but the difference is much greater with BzH.  BzH and VI always favor formation of II.  PhCH:CHCH:CHCOEt, m. 55-6°, was prepd. by a modified Wittig reaction; semicarbazone m. 200-1°; phenylhydrazone m. 89-90°.  4-(2-Furyl)-3-methyl-3-buten-2-one, b10 114-15°, and 5-(2-furyl)-4-penten-3-one, b13 122-4°, were also prepd. by this method.  Orientation of condensation was postulated to be regulated by the steric requirement.  s-Cis and s-trans conformations of some of the unsatd. ketones were detected by ir spectra. 


A study of the reaction of butanone with benzaldehyde and p-nitrobenzaldehyde.    
Jung, Duksang.    Cheju Univ.,  Cheju,  S. Korea.  
Nonmunjip - Cheju Taehak  (1982),  14  27-31.
Journal  written in Korean.   
Abstract
In alk. medium, the reaction of p-O2NC6H4CHO and MeCOEt gave three hydroxy ketones, indicating that both Me and CH2 positions were attacked to a comparable extent.  Dehydration of the intermediate hydroxy ketones is a slow step.  In acid medium, however, the addn. step of the reaction was selective, giving only 1 isomer.  Similarly, in alk. medium, PhCH(OH)CH2COEt (I) and PhCH(OH)CHMeCOMe (II), hydroxy ketone intermediates from the reaction between BzH and MeCOEt, gave PhCH:CHCOEt (III).  Treating I and II with acid gave III and PhCH:CMeCOMe, resp., with no evidence of rearrangement. 


These journal articles detail its synth also.

Double Michael addition reactions of some new 1,5-diaryl-2-alkyl-1,4-pentadien-3-ones: Part II.
Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  (2001),  40B(8),  667-673.

RuCl3 catalyzes aldol condensations of aldehydes and ketones.   
Tetrahedron  (1998),  54(32),  9475-9480. 

Synthesis of isoquinoline-1,3-dicarboxylic acid.    
Chin. Chem. Lett.  (1999),  10(11),  907-910. 
(in english)

Here is the baseic addition

Kinetics of condensation of benzaldehyde and its derivatives with acetone and methyl ethyl ketone catalyzed by aluminum oxide.   
Collect. Czech. Chem. Commun.  (1980),  45(6),  1812-19.
Journal  written in English.
Abstract
The pseudo-1st-order aldol condensation kinetics of RC6H4CHO (R = H, 4-Me, 3-MeO, 4-MeO, 3-Cl,4-Cl) with excess Me2CO over Al2O3 at 60-160° and the pos. r indicated that the addn. step, to give hydroxy ketone, is rate detg.  r Decreases with increasing temp.; the isokinetic temp. is 449.8K.  At 60-90° the retroaldol reaction of PhCH(OH)CH2Ac is minor and the dehydration to PhCH:CHAc is major; the proportion of dehydration-retroaldol reaction increases with increasing solvent polarity and decreases with increasing temp.  The condensation of PhCHO with MeCOEt at 90-160° gives mostly PhCH:CHCOEt in a reaction catalyzed by the basic sites on Al2O3; the minor product, PhCH:CMeAc, formation is catalyzed by the acidic Al2O3 sites. 


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foxy2

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Re: New method for P2P
« Reply #2 on: December 09, 2001, 05:16:00 PM »
This review would probably bee very helpful.

The Baeyer-Villiger oxidation of ketones and aldehydes.
Krow, Grant R.
Org. React. (N. Y.)  (1993),  43  251-798.  
Abstract
A review with >1092 refs. 


Refs for the second one(partial of this article)

Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations
Nature 412, 423 - 425 (2001)
 
The Baeyer–Villiger oxidation, first reported more than 100 years ago1, has evolved into a versatile reaction widely used2 to convert ketones—readily available building blocks in organic chemistry—into more complex and valuable esters and lactones. Catalytic versions of the Baeyer–Villiger oxidation are particularly attractive for practical applications, because catalytic transformations simplify processing conditions while minimizing reactant use as well as waste production. Further benefits are expected from replacing peracids, the traditionally used oxidant, by cheaper and less polluting hydrogen peroxide3. Dissolved platinum complexes4 and solid acids, such as zeolites5, 6 or sulphonated resins7, efficiently activate ketone oxidation by hydrogen peroxide. But these catalysts lack sufficient selectivity for the desired product if the starting material contains functional groups other than the ketone group; they perform especially poorly in the presence of carbon–carbon double bonds. Here we show that upon incorporation of 1.6 weight per cent tin into its framework, zeolite beta acts as an efficient and stable heterogeneous catalyst for the Baeyer–Villiger oxidation of saturated as well as unsaturated ketones by hydrogen peroxide, with the desired lactones forming more than 98% of the reaction products. We ascribe this high selectivity to direct activation of the ketone group, whereas other catalysts first activate hydrogen peroxide, which can then interact with the ketone group as well as other functional groups.


When trying to avoid the use of peracids for the Baeyer–Villiger reaction, the methodology developed up to now involved catalysts able to activate hydrogen peroxide, H2O2. Amongst homogeneous catalysts, complexes of molybdenum8 and rhenium9 have been shown to activate H2O2, but their turnover numbers (TONs) and selectivities are relatively low (TONs are below 20 for overall reaction times ranging from 12 to 24 hours). Pt complexes achieve TONs of about 50 within 5 hours, but are not chemoselective when other functional groups are present10. Concerning heterogeneous catalysts, supported Pt complexes11 and TS-112 have been used, but have shown only limited activity and selectivity, respectively. Acid zeolites such as H-beta and USY activate hydrogen peroxide for the Baeyer–Villiger oxidation, but show selectivities of less than 60–70% (ref. 5). MeReO3 (ref. 13), TS-13 and Pt complexes14 are excellent epoxidation catalysts in the presence of H2O2 and consequently, epoxidation is favoured over the Baeyer–Villiger oxidation when using unsaturated ketones as starting material.

References
1. Baeyer, A. & Villiger, V. Einwirkung des Caro'schen Reagens auf Ketone. Chem. Ber. 32, 3625-3633 (1899).
2. Renz, M. & Meunier, B. 100 years of Baeyer-Villiger oxidations. Eur. J. Org. Chem. 737-750 (1999).
3. Arends, I. W. C. E., Sheldon, R. A., Wallau, M. & Schuchardt, U. Oxidative transformations of organic compounds mediated by redox molecular sieves. Angew. Chem. Int. Edn Engl. 36, 1145-1163 (1997).
4. Strukul, G. Transition metal catalysis in the Baeyer-Villiger oxidation of ketones. Angew. Chem. Int. Edn Engl. 37, 1198-1209 (1998).
5. Fischer, J. & Hölderich, W. F. Baeyer-Villiger-oxidation of cyclopentanone with aqueous hydrogen peroxide by acid heterogeneous catalysis. Appl. Catal. A 180, 435-443 (1999).
6. Chang, C. D. & Hellring, S. D. Production of lactones and omega-hydroxycarboxylic acids. US Patent No. 4870192 (1996).
7. Hoelderich, W., Fischer, J., Schindler, G. -P. & Arntz, D. Preparation of lactones by Baeyer-Villiger oxidation of cyclic ketones. German Patent DE 19745442 (1999).
8. Jacobson, S. E., Tang, R. & Mares, F. Oxidation of cyclic ketones by hydrogen peroxide catalysed by group 6 metal peroxo complexes. J. Chem. Soc. Chem. Commun. 888-889 (1978).
9. Herrmann, W. A., Fischer, R. W. & Correia, J. D. G. Multiple bonds between main-group elements and transition metals. Part 133. Methyltrioxorhenium as a catalyst of the Baeyer-Villiger oxidation. J. Mol. Catal. 94, 213-223 (1994).
10. Gavagnin, R., Cataldo, M., Pinna, F. & Strukul, G. Diphosphine-palladium and -platinum complexes as catalysts for the Baeyer-Villiger oxidation of ketones: effect of the diphosphine, oxidation of acyclic ketones, and mechanistic studies. Organometallics 17, 661-667 (1998).
11. Palazzi, C., Pinna, F. & Strukul, G. Polymer-anchored platinum complexes as catalysts for the Baeyer-Villiger oxidation of ketones: preparation and catalytic properties. J. Mol. Catal. A 151, 245-252 (2000).
12. Bhaumik, A., Kumar, P. & Kumar, R. Baeyer-Villiger rearrangement catalysed by titanium silicate molecular sieve (TS-1)/H2O2 system. Catal. Lett. 40, 47-50 (1996). 
13. Herrmann, W. A. Essays on organometallic chemistry, VII. Laboratory curiosities of yesterday, catalysts of tomorrow: organometallic oxides. J. Organomet. Chem. 500, 149-150 (1995).
14. Frisone, M. D. T., Pinna, F. & Strukul, G. Baeyer-Villiger oxidation of cyclic ketones with hydrogen peroxide catalyzed by cationic complexes of platinum(II): selectivity properties and mechanistic studies. Organometallics 12, 148-156 (1993).


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foxy2

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Re: New method for P2P
« Reply #3 on: December 09, 2001, 05:33:00 PM »
Not sure if this one will work, but there are some other reactions in there that might bee of interest to bees.  Benzaldehydes to phenols.

Baeyer-Villiger oxidation of b-aryl substituted unsaturated carbonyl compounds with hydrogen peroxide and catalytic selenium dioxide.
Synth. Commun.  (1995),  25(14),  2121-33.

Abstract
A simple and cheap oxidative procedure using 30% H2O2 and catalytic SeO2 allows to transform 2-aralkylidenecycloalkanones and hydroxy- or alkoxybenzaldehydes to give, in high yields, enol lactones and aryl formates, resp. 

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foxy2

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Re: New method for P2P
« Reply #4 on: December 09, 2001, 06:03:00 PM »
Yes a-Methylcinnamaldehyde should work in the Oxidation also.



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Rhodium

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Re: New method for P2P
« Reply #5 on: December 10, 2001, 11:54:00 PM »
This synthesis might aid the people trying to do the condensation step:

http://www3.springer-ny.com/chedr/sample/13smi897.htm


twodogs

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Re: New method for P2P
« Reply #6 on: December 11, 2001, 03:36:00 AM »
With all due respect Rhodium, the reference that you have given would not help any one with the condensation that I have mentioned. ie between benzaldehyde and butanone (methyl ethyl ketone).
Your reference concerns the condensation of aromatic aldehydes and acetone under basic conditions,
The literature on aldol condensations involving these reactants established the following:
C6H5CHO + CH3COCH3 + NaOH         ------> C6H5CH=CHCOCH3 and
C6H5CHO + CH3CH2COCH3 + NaOH -----> C6H5CH=CHCOCH2CH3 but
C6H5CHO + CH3CH2COCH3 + HCl     -----> C6H5CH=C(COCH3)CH3.
The condensation to get methyl phenyl butenone  needs to be done under acidic conditions. There is a French reference somewhere that states that the condensation can be done by reluxing equal volume amounts of benzaldehyde and butanone with hydrochloric acid and there are also references using  H2SO4. I have tried both of these and did not get the result that I did using dry HCl gas.

Rhodium

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Re: New method for P2P
« Reply #7 on: December 11, 2001, 04:30:00 AM »
Okay, I'll shut up when it comes to aldol chemistry again. That's not my field.

lugh

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Re: New method for P2P
« Reply #8 on: December 12, 2001, 12:32:00 PM »

Interesting. What is the reference for the first condensation reaction?




The references from the article on the first condensation from Organic Reactions 16 (entirely on aldol condensations) are from Rec Trav Chem 84 17 & 979 (1968)


Rhodium

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Acidic condensation of Benzaldehyde & MEK
« Reply #9 on: November 17, 2003, 02:29:00 AM »
Benzaldehyde + methyl ethyl ketone -> 2-acetyl-propenylbenzene

Acid Catalyzed (HCl or H2SO4):

C.R.Hebd.Seances Acad.Sci. 226, 1095 (1948)
C.R.Hebd.Seances Acad.Sci. 226; 1948; 500.
Indian J.Chem.Sect.B 40(8), 667-673 (2001)
Bull.Chem.Soc.Jpn.; 69; 9; 1996; 2633-2638.
Bull.Soc.Chim.Fr.; <4>47; 1930; 195,199,200;
Bull.Soc.Chim.Fr.; 1970; 1497-1502.
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.
Pol.J.Chem.; EN; 52; 1978; 2233-2241.
Pol.J.Chem.; EN; 53; 1979; 849-853.
Gazz.Chim.Ital.; 67; 1937; 440, 442.
Gazz.Chim.Ital.; 63; 1933; 199, 202.
Ann.Sci.Univ.Jassy,Sect.1; 16; 1931; 536,540,542.
Arch.Pharm.(Weinheim Ger.); GE; 309; 1976; 969-978.
J.Pharm.Sci.; 64; 1975; 241-248.
Can.J.Chem.; 49; 1971; 105-117.
Chem.Ber.; 35; 1902; 970.
Ann.Chim.(Paris); <12>4; 1949; 242;

J. Amer. Chem. Soc. 65, 1824 (1943)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/phcho-mek-aldol.pdf)
Tetrahedron: Asymmetry 6(9), 2143-2144 (1995) "Enones were prepared from the reaction of the corresponding aryl aldehyde with 2-butanone in 1M H2SO4 of acetic acid solution."

Ruthenium(III)Chloride (90% yield):

Tetrahedron 54(32), 9475-9480 (1998)
DOI:

10.1016/S0040-4020(98)00575-4






Phenylacetone by Bayer-Villiger Oxidation of 2-acetyl-1-phenylprop-1-ene
Boeeseken & Jacobs
Recl. Trav. Chim. Pays-Bas 55, 786 (1936)

Peracetic acid treatment of 2-acetyl-propenylbenzene (3-methyl-4-phenyl-but-3-en-2-one) below 30°C resulted in the formation of phenylacetone enol acetate (2-acetoxy-1-phenylprop-1-ene), mp 131°C and bp 103°C/3mmHg. Heating the crude reaction mixture with aqueous HCl at 80°C gave phenylacetone.

bio

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JACS article
« Reply #10 on: November 17, 2003, 02:28:00 PM »
This is fantastic yield increase from 60-94% using 1 to 1 molar ratio. I will try it in a few days. The twodogs procedure uses 2.2 mole MEK to 1 mole PhCHO.

What was not stated in the synthesis part was the temp used when HCL gasing. There is a footnote to this article saying they followed this procedure.,,,,,,,,,,,(5) Muller and Harries, Ber., 36, 9BG (1902).,,,,,,,,,,,,if anyone could find this it would be very helpfull.

I think perhaps the reason my recent yield was so much better (79%) is that I went slower to keep the temp below 5deg and based on earlier results added HCL to compensate for the weight not gained from what was passed. This resulted in a more saturated solution. The amount given (.58 mole HCL) does result in a saturated solution but it is easy to have a lot gas off. I also left it in the ice bath overnight to warm up.

Now if we can only find a non-exotic catalyst for the oxidation this method begins to get very attractive.

Rhodium

  • Guest
More MEK/Benzaldehyde condensation refs
« Reply #11 on: February 10, 2004, 04:31:00 AM »
Ueber die Condensation von Aethylmethylketon mit Benzaldehyd
C. Harries, G. H. Müller

Chem. Ber. 35, 966-971 (1902)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/mek-aldol-ber.pdf)

Summary
A mixture of 100g methyl ethyl ketone and 140g benzaldehyde is cooled in an ice/salt bath, and saturated with dry hydrogen chloride gas. The reaction mixture turns red, and is allowed to stand for 1-2 days, after which time the oily product is shaken with dilute sodium hydroxide, washed with water and dissolved in diethyl ether. From the ether the product crystallizes in large needles, which smells of camphor. The yield is quantitative. The ketone can be recrystallized from petroleum ether (1g is soluble in 8-9 mL at 20°C) to give fine needles, mp 38°C/bp 127-130°C/12mmHg.
____ ___ __ _

The Condensation of Phenolic Aldehydes and Their Ethers with Methyl Ethyl Ketone
Kenji Iwamoto

Bull. Chem. Soc. Jap. 2, 51-57 (1927)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/mek-aldol-bcsj.pdf)

Summary
Condensation of benzaldehydes with MEK under basic conditions (yielding PhCH=CHCOCH2CH3) and acidic (yielding PhCH=C(CH3)COCH3). The reactions are performed with 4-methoxy-, 4-hydroxy-, 3-methoxy-4-hydroxy-, and 3,4-methylenedioxy-benzaldehyde.


Rhodium

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Peracid oxidation of unsaturated ketones
« Reply #12 on: February 11, 2004, 01:03:00 PM »
Here are all Boeseken's articles on the topic of peracid oxidation of unsaturated ketones, including the one mentioned in

Post 471343

(Rhodium: "Acidic condensation of Benzaldehyde & MEK", Novel Discourse)

The articles mentioned in

Post 246863

(lugh: "Re: New method for P2P", Novel Discourse)
does not contain any experimental parts, only theoretical studies of benzalacetones.


Sur L'Iso-Phényl-Vinyl-Acetate, C6H5CH=CHOAc, Produit de L'oxydation de la Mono-Benzalacétone par les Peracides
J. Boeseken, A. Kremer

Rec. Trav. Chim. 50, 827-832 (1931)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/boeseken1931.pdf)
____ ___ __ _

Le Produit de L'oxydation de la Benzalacétone par L'acide Peracétique
J. Boeseken, A. L. Soesman

Rec. Trav. Chim. 52, 874-880 (1933)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/boeseken1933.pdf)
____ ___ __ _

L'oxydation par les Peracides de la Double Liaison à Côte d'un Groupe Carbonyle
J. Boeseken, J. Jacobs

Rec. Trav. Chim. 55, 786-790 (1936)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/boeseken1936a.pdf)
____ ___ __ _

L'oxydation des 1,3-Dicétones par L'acide Peracétique
J. Boeseken, J. Jacobs

Rec. Trav. Chim. 55, 804-814 (1936)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/boeseken1936b.pdf)


chilly_willy

  • Guest
about this method..
« Reply #13 on: February 16, 2004, 04:15:00 PM »
First of all I want to say that twodogs procedure works just as described.  I also want to mention that somebee has tried both aldehyde:ketone aldol ratios mentioned. Literature 1:1, and twodogs 1:2.2.  The yields from both trials were roughly the same 220-230g from 200g aldehyde.  The only difference was the latter contained a larger MEK forerun upon distillation.  The 1:1 ratio experiment might have yeilded a bit more (20-30g) if the experimenter was willing to relocate the heavy "tar" layer into a smaller flask and finish off the distillation..but it just didnt seem worth the time.
Two questions arise and I thought maybe to just include them in this post instead of starting a new thread.
1. Will heating the twodogs baeyer-villiger product (P2P enol ester) with 33% HCl perform the same function as the saponification step to arrive at P2P??
2.  If not, can another alcohol such as IPA, or MeOH be substituted for the 95% EtOH (everclear) in the saponification step?  Ironically the ethanol is probably the most expensive chem needed in the whole procedure ($13 750mL).


bio

  • Guest
one to one ratio
« Reply #14 on: February 16, 2004, 06:10:00 PM »
The only thing I can see that bio has been doing (not reading german)different is that Harries et al saturated at salt bath temp and let sit for one to 2 days. So this was done at minus 5 degrees whereas previous runs were plus 5 degrees 21.2g/mole HCl passed about 18 absorbed. It did hold about 3 grams per mole more HCl and has not been worked up yet. Now twodogs stated too much HCl promoted polymerization so we will see. The 1:1.05 trial at 5 deg sat 10 hours and crystallized  nicely without distilling. First crop weighed in at 75g and the other is in the freezer. 1st crop washed with 96% EtOH will not need recrys. Looks as clean as the fractionated stuff.

Damn, Chilly are you paying alcohol tax? 96% EtOH here is $1.20 in then discount stores a little more in the drug stores. Actually cheaper than the tech stuff from the chem house and you get a nice heavy HDPE bottle to play with. Seems like no one else is interested in this simple non suspicious procedure. I wonder why?

I think the french articles discuss the concentration of HCl to saponify but I can't read it and what I can decipher may bee wrong. I'll ask bio to pst the pertinent paragraphs and maybee some kind frenchbee can translate. It's actually very short did you see it? Look at the 1936 Jacobs one.

bio

  • Guest
one to one ratio
« Reply #15 on: February 17, 2004, 11:50:00 PM »
OK, the procedure done per the Berliner article (as much as could be deciphered anyway), details above, sat 39 hrs at ambient (ca 20deg). Washed with NaOH separated all but the last few drops to let settle a while. When ready to do the water wash noticed the crystals had already set up in the funnel. Heating the funnel now to melt the stuff. This has never happened before, hopefully a portend of the greater yield.

Bwiti

  • Guest
HBr Gas ? ?
« Reply #16 on: February 22, 2004, 09:48:00 PM »
"There is a French reference somewhere that states that the condensation can be done by reluxing equal volume amounts of benzaldehyde and butanone with hydrochloric acid and there are also references using  H2SO4. I have tried both of these and did not get the result that I did using dry HCl gas."

  Perhaps anhydrous HBr gas could be used instead? Dry HBr is easier for me to make.


hoffman

  • Guest
Oxone
« Reply #17 on: March 28, 2004, 06:09:00 PM »
You would think that oxone(Potassium Peroxymonosulfate) might bee good here for the per-acid.

2 cents,
This is a reaction deserves another look,!

hoff

Megatherium

  • Guest
Toluene ---> P2P with oxone & MEK?
« Reply #18 on: April 01, 2004, 06:42:00 AM »

You would think that oxone(Potassium Peroxymonosulfate) might bee good here for the per-acid.

2 cents,
This is a reaction deserves another look,!






Toluene can be oxidized to benzaldehyde with persulphate:

Post 208719

(Osmium: "Re: The easiest synth of benzaldehyde from toluene", Chemistry Discourse)


Condense the prepared benzaldehyde with MEK and do the Baeyer-Villiger with K2S2O8 - H2SO4 (ref.: Billups, Kramer, Lastomirsky: J. Org. Chem. (1970) vol 35, p 3080)

Hydrolize et voilà.

Megatherium

  • Guest
I have only access to the first page of this...
« Reply #19 on: April 04, 2004, 03:13:00 PM »
I have only access to the first page of this article online  ::)

The abstract says:
'Solutions of K2S2O8 in 20 - 60 % H2SO4 are advantageous for the Baeyer - Villiger oxidation of ketones.  Yields are quantitative and the differences in migratory aptitudes are larger than those found with other peracids.'

I guess the enol ester just will rearrange in situ to the P2P in the acidic environment (1 pot).
 
Now, I have been informed that somebee wants to try out this reaction.  Unfortunately, I can't get the journal in my hands until next month.

It would really surprise me if there was nobee with online access to the full journal.  I 'm sure the involved bee will produce a nice write-up for the hive collective.