Strange Wacker?

[psychokitty]

Process for the manufacture of carbonyl compounds 
Patent Number: GB895843 
Publication date: 1962-05-09 
Inventor(s):  
Applicant(s): CONSORTIUM ELEKTROCHEM IND 
Requested Patent:  GB895843 
Application Number: GB19580028150 19580902 
Priority Number(s): DEX895843 19570906 
IPC Classification:  
EC Classification: C07C45/28, C07C45/30, C07C45/34, C07C205/45, C07C317/44 
Equivalents:  

--------------------------------------------------------------------------------
Abstract
--------------------------------------------------------------------------------
 
Aldehydes and ketones are obtained by treating an organic compound containing one or more hetero atoms and one or more carbon to carbon double bonds, with an aqueous solution of a compound of a platinum group metal at 0 DEG C.-250 DEG C. Hetero atoms specified are oxygen, sulphur, halogens, and nitrogen. Metals specified are palladium and rhodium. The halides sulphates, phosphates, acetates, and corresponding complexes of these metals may be used. An oxidising agent is preferably also present in the reaction mixture, e.g. oxygen gas, persulphates, hydrohalic acids or salts, chromates, and other oxo-metallates. Salts of polyvalent metals such as iron and copper may also be present. The reaction is preferably carried out at a pH of 0-2, and the catalyst solution may be periodically reactivated by oxidation with, e.g. oxygen. The reactants may be brought into active contact by shaking, sprinkling, vibrating, or other methods. The process may be carried out at pressures of 1-50 atmospheres in trickling towers, columns of filler bodies, or vessels provided with stirrers. Examples are given of the production of p-methoxy - phenyl acetone from 4 - methoxy - 1 - propenyl benzene; 1,3,5-triacetyl benzene by ring closure of acetyl acetaldehyde which is first obtained from crotonaldehyde; acetaldehyde from acrylic acid, vinyl bromide, b -bromo styrene, and a -bromo-acrylic acid; acetone from crotonic acid, a -methoxy crotonic acid, 1-bromo propene, 2-chloropropene, a -chlorocrotonic acid, and crotonic acid amide; propionaldehyde from methycrylic acid, a -methacrylic acid amide, and allylamine; acetophenone from cinnamic acid, ethyl cinnamate, a -chlorostyrene, b -bromo-styrene, a -bromocinnamic acid, and cinnamic acid amide; pyruvic acid from maleic acid; methyl ethyl ketone from tiglic acid, a ,b -pentenic acid, 1-bromo butene (1), a -bromo-a ,b -pentenic acid and a ,b -pentenic acid amide; succinic acid aldehyde from itaconic acid; ethylidene acetone from sorbic acid; a -methyl acrolein and isobutyraldehyde from 1-chloro-2-methyl-propene (1); methyl glyoxal from allyl bromide, allyl chloride, 2,3-dibromopropene, and 1,3-dichloro-propene (1); pyruvonitrile from acrylonitrile; acrolein from allyl alcohol; p-methoxy acetophenone from p-methoxy styrene; 3,4-dioxymethylenebenzyl-methyl ketone from iso-safrole; n-propyl, n-butyl, and n-amyl methyl ketones from the corresponding a ,b -unsaturated acids, and their a -bromo derivatives; propiophenone from a -chloro-b -methyl styrene; benzyl methyl ketone from 2-chloro-1 or 3-phenyl propene (1); g -bromo-propyl methyl ketone from 1-bromopentene (4); p-chloroacetophenone from p-chlorostyrene and p-chloro-cinnamic acid; m-nitroacetophenone from m-nitro-styrene and m-nitrocinnamic acid methyl - [butanone - (2) - yl - (4)]-sulphone from the corresponding butene compound. Specifications 876,025 and 886,157 are referred to.
 

[psychokitty]

Well lookie fucking here--yet another fine example of fellowbee neglect. 

To cut right to the chase, this is a strange wacker. PdCl2 (formed from palladium metal in aqua regia) is used in a biphasic aqueous acidic solution to convert isosafrole into MD-P2P in--this is what's strange--90% or so yields with a 50% or so conversion (??).  So I really don't know if the yields are good or not.  But supposedly the synthesis is quite versatile in terms of using other noble metal salts to carry out the same oxidation.  And what's with the use of a propenyl benzene instead of an allylbenzene?  Like I said:  Strange. 

Sooooooo, I simply thought that the details to this "strange wacker" patent were interesting enough to post . . . unlike what seems to be every other member of the Hive. 

Peeuuww!!!!

[Rhodium]

It is very interesting, but you are impatient - not everybody logs on every day

[obia]

I read it as 50% of the isosafrole was consumed producing a mixture of products containing 90% mdp2p and 10% other crap, so the overall yield based on the isosafrole quantity and without recycling unused isosafrole is 50% * 90% = 45%
yield is ok if one recovers the unused isosafrole

[psychokitty]

Process for the manufacture of aldehydes and ketones and catalyst therefor 
Patent Number: GB878777 
Publication date: 1961-10-04 
Inventor(s):  
Applicant(s): CONSORTIUM ELEKTROCHEM IND 
Requested Patent:  GB878777 
Application Number: GB19580022370 19580711 
Priority Number(s): DEX878777 19570723 
IPC Classification:  
EC Classification:  
Equivalents:  

--------------------------------------------------------------------------------
Abstract
--------------------------------------------------------------------------------
 
By means of an aqueous catalyst solution containing a compound of a Pt metal, a salt of a polyvalent transition metal excepting the Pt group (e.g. of Cu, Fe or Mn) and halogen ions in 60 to below 100% of the amount present if all metal salts were present as their highest stable halides, carbonyl compounds are prepared from an olefin of the same number of carbon atoms, by contacting with oxygen. The reaction conditions are preferably:-(a) pH 0-2; (b) 1-50 atm. gauge; (c) 50-150 DEG C. In examples, ethylene, propylene, butylene and allylbenzene were converted, respectively, to acetaldehyde, acetone, methyl ethyl ketone and benzyl methyl ketone. Catalyst constitutents specified are CuCl, CuCl2, Cu(acetate)2, CuBr2, FeCl3, Fe(OH)2acetate, MnCl2, PdCl2, PdBr2, HCl and HBr. Specifications 876,024 and 876,025 are referred to.ALSO:By means of an aqueous catalyst solution containing a compound of a Pt metal, a salt of a polyvalent transition metal excepting the Pt group (e.g. of Cu, Fe or Mn) and halogen ions in 60 to below 100% of the amount present if all metal salts were present as their highest stable halides, carbonyl compounds are prepared from an olefin of the same number of carbon atoms, by contacting with oxygen. The reaction conditions are preferably: - (a) pH 0-2; (b) 1-50 atom gauge; (c) 50-150 DEG C. In examples, ethylene, propylene, butylene and allylbenzene were converted, respectively, to acetaldehyde, acetone, methyl ethyl ketone and benzyl methyl ketone. Catalyst constituents specified are CuCl, CuCl2, Cu(acetate)2, CuBr2, FeCl3, Fe(OH)2acetate, MnCl2, PdCl2, PdBr3, HCl and HBr. Specifications 876,024 and 876,025 are referred to.
 

[burrowing_owl]

PATENT ABSTRACTS OF JAPAN
Publication number: 59-190949
Date of publication of application: 29.10.1984
------------------------------------------------------------------
Application number: 58-064504
Applicant: UBE IND LTD
Date of filing: 14.04.1983
Inventor: ENOMIYA TAKUJI
----------------------------------------------------------------------
PRODUCTION OF 1-PHENYL-2- ACETOXYPROPENE
Abstract:
PURPOSE: To obtain industrially and advantageously the titled compound useful as an intermediate for agricultural  chemicals  and medicines, by reacting a 1-phenylpropene with acetic acid in the presence of palladium acetate and an alkali.
CONSTITUTION: A 1-phenylpropene of the formula (R is H, hydroxy group, halogen, etc.) is reacted with acetic acid in the presence of paladium acetate and an alkali, eg. sodium acetate, usually at 10W100C for 0.5W5hr under ordinary or higher pressure to give  the aimed substance of the formula.
EFFECT: 1-(4-Hydroxy-3-methoxyphenyl)-2-acetoxypropene is hydrolized and converted into 4-HYDROXY-3-METHOXYPHENYLACETONE which is a raw material for producing L-a-methyldopa useful as a hypotensive agent.
---------------------------------------------------------------------------

I would be indebted to anyone  who could translate this puppy.

[foxy2]

JP59190949
Abstract
2,3,4-RR1R2C6H2CH:CMeOAc I (R, R1, R2 = H, H, OH; OH, H, H; H, OH, OH; H, OH, OMe; H, Me, OH; Cl, H, OH) were prepd. by acetoxylation of 2,3,4-RR1R2C6H2CH:CHMe (II) with HOAc in the presence of Pd(OAc)2 and alkali.  Thus, a mixt. of II (R = R1 = H, R2 = OH) 0.1, NaOAc 0.01, and Pd(OAc)2 0.11 mol in 500 mL HOAc was heated 1 h at 65° to give 58% I (R = R1 = H, R2 = OH). 


Those who give up essential liberties for temporary safety deserve neither liberty nor safety