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PSY420
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| Joined: 30 Jun 2005 |
| Posts: 30 |
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1174.16 Points
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yet another neat way from BA to P2P
Fri Jul 01, 2005 5:01 pm |
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I'm not into unsubstituted amphetamines so I didn't bother to get the refs for [1] ...
[1] J.Chem.Soc., 43; 408 (1883) AcOH, sodium propionate
Helv. chim. acta, 11; 982-998 (1928) Et3N, propionic acid
Chem. Ber., 20; 618 (1887) propionic anhydride, NaOAc
[2] J. Org. Chem., 51,10;1925-1926 (1986)
A stirred slurry of trans-cinnamic acid (111.0 g 0.75 mol) in aceton (515 mL) was treated first with NaHCO3 (274 g 3.26 mol) and then carefully with water (515 mL) The resulting thick mixture was treated dropwise , over 1.5 h, with a soln. of oxone (2 KHSO5 * KHSO4 * K2SO4) (421g, contains 1.825 equiv. of KHSO5) in 4 x 10^-4 M aqu. Na2-EDTA (1610 mL).
During this addition the reaction temperature was maintained at 24 – 27 °C by using a water bath and the rxn pH at ca. 7.4. After the addition was complete the mixture was stirred an additional 0.5 h and cooled to ca. 10°C. The reaction was acidified with conc. HCl (ca. 140 mL) to pH 2 while the temperature was maintained at 10°C and then treated w/ EtOAc (1.0 L) followed by rapid stirring. The mixture was filtered to remove insoluble salts, and the organic layer was removed. The aquaeous layer was extracted with EtOAc (500 mL), and the combined organic layers were washed once with saturated aqu. NaCl (200 mL) dried over MgSO4 and concentrated in vacuo from a 40°C bath. Toward the end of the concentration absolute EtOH was added (to keep the acid from crystallizing out) and concentration was continued until most of the solvent was removed.The yellowish oily residue was dissolved in absolute EtOH (500 mL) cooled on ice and treated with a soln. of KOH (56 g 1 mol) in abs. EtOH (250 mL). The resulting thick slurry was filtered and the solids were washed with EtOH. The filter cake was resuspended in fresh abs. EtOH (750 mL) , filtered, washed with EtOH, and dried in a 50 °C oven to give trans-ß-phenylglycidic acid (139 g 92%) as a white powder.
yield for our target compound was 92 %, rxn time : 2,5 h, scale was 0.5 mol. mp 67-68 (lit: 68-69)
[3] J.Org.chem.USSR (Engl.Transl.), 19; 1709-1714 (1983)
The expoxy acid was heated at 200-220°C for 3h. The product was cooled, a 10% solution of K2CO3 was added to an alkaline reaction, the mixture was extracted with ether, and the extract was dried with MgSO4. After distillation of the ether the residue was distilled. The P2P (77.6% yield) had bp 110° @ 2 mmHG and refractive index (D,20°C) of 1.5090.
--PSY420-- |
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 7:45 pm |
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>> A stirred slurry of trans-cinnamic acid (111.0 g 0.75 mol) in ....
C'est un typo? should be alpha-methyl-trans-cinnamic acid
Your find est très elegant! Un route alternative for le alpha-methylcinnamic acid uses le sodium hydride:
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a-Methylcinnamic acid.
A vigorously stirred suspension of 9.1 g. of sodium hydride in 125 ml. of methyl propionate was cooled in ice and treated with 0.45 ml. of absolute ethanol, then with 31.84 g. of benzaldehyde in 50 ml. of methyl propionate during 10 min. The ice bath was removed after one hour, replaced as soon as the vigorous reaction started, then removed again, and stirring was continued for another 2 hr. The organic layer was separated, after cautious addition of 28 ml. of acetic acid, then of 100 ml. of water, and the aqueous phase extracted with ethyl acetate. The combined ester solutions were washed with N hydrochloric acid and with sodium chloride solution, dried with sodium sulfate, and evaporated in vacuo. The residual ester was refluxed with 33.6 g. of potassium hydroxide in 60 ml. of water and 240 ml. of methanol for one hour. The solution was concentrated, diluted with water to ca. 500 ml., acidified with 6 N hydrochloric acid, chilled overnight, and the collected solid was washed with ice water; yield 35.67 g. (73%), m.p. 75-81°C'. The acid crystallized from hexane in colorless prisms, m.p. 80.5-81.0°C (lit[24] m.p. 81-82°C).
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https://www.synthetikal.com/Rhodiums_pdfs/chemistry/alpha-methylhydrocinnamic.html
Let's hope le old J.Chem.Soc. paper that uses NaOPr and AcOH holds some promise.. |
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Vitus
Psychoscientist
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| Joined: 19 Apr 2005 |
| Posts: 72 |
| Location: Dunwich |
2608.18 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 8:27 pm |
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Here are some more refs:
Alpha-methylcinnamic acid
From benzal chloride and sodium propionate:
Chem. Ber. 36 (1903) 4316
Chem. Ber. 38 (1905) 2316
Justus Liebigs Ann. Chem. 227 (1885) 248
From 3-methyl-4-phenylbut-3-ene-2-one (aldol BA + MEK + acid)
using hypochlorite:
Bull. Chem. Soc. Jpn. 27 (1954) 131
Zh.Prikl.Khim.(Leningrad) 24 (1951) 1098; Chem.Abstr. (1952) 7538
Chem. Ber. 35 (1902) 3552
From benzaldehyde, sodium propionate and AcOH (200°C):
Chem. Ber. 16 (1883) 1437
From benzyl chloride and methylmalonic acid diethyl ester:
Collect. Czech. Chem. Commun. 48, 1 (1983) 60-70
From benzenediazonium chloride and sodium methacrylate:
Gazz. Chim. Ital. 78 (1948) 524, 533
Patents
FR1385727 (Chem.Abstr. 63, 610f (1965))
CH592598, DE2449928 (Chem.Abstr. 83, 192925)
Related papers that might be of interest:
Collect. Czech. Chem. Commun. 44 (1979) 183,186
Acta Pol. Pharm. 18 (1961) 177,178; Chem.Abstr. 56, 11470 (1962)
Chim. Ther. 8 (1973) 202
Cesk. Farm. 22 (1973) 388
Bull. Soc. Chim. Fr. (1970) 738
J. Org. Chem. 31 (1966) 4061-4066
J. Am. Chem. Soc. 94 (1972) 2520
J. Chem. Soc. Perkin Trans. 2 (1972) 1434,1439
J. Org. Chem. 38 (1973) 2945,2948
J. Am. Chem. Soc. 88 (1966) 5213,5214
J. Org. Chem. 42 (1977) 3903
J. Am. Chem. Soc. 94 (1972) 2520
J. Agric. Food Chem. 25 (1977) 1401,1402
J. Org. Chem. 41, 9 (1976) 1545,1547
J. Org. Chem. 38 (1973) 2554
Zesz. Nauk. Politech. Slask. Chem. 25 (1964) 1,21,93; Chem.Abstr. 63, 4253
Recl. Trav. Chim. Pays-Bas 89 (1970) 491,492,494
Can. J. Chem. 50 (1972) 2851-2858
Bull. Soc. Chim. Fr. (1966) 2653-2658
J. Org. Chem. 35 (1970) 666
Bull. Soc. Chim. Fr. (1975) 743-750 |
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joe_aldehyde
huxleys associate
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| Joined: 06 Apr 2005 |
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5653.90 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 9:19 pm |
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From benzaldehyde, sodium propionate and AcOH (200°C):
Chem. Ber. 16 (1883) 1437
somebody please get this one. got loads of benzaldehyde and sodium propionate 
Last edited by joe_aldehyde on Fri Jul 01, 2005 9:22 pm; edited 1 time in total |
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Vitus
Psychoscientist
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| Joined: 19 Apr 2005 |
| Posts: 72 |
| Location: Dunwich |
2608.18 Points
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PSY420
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| Joined: 30 Jun 2005 |
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1174.16 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 9:22 pm |
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>>"C'est un typo? should be alpha-methyl-trans-cinnamic acid"
Non ce n'est pas. They just use trans-cinnamic acid as their example for demonstration-purposes. The key phrase is
"yield for our target compound was 92 %, rxn time : 2,5 h, scale was 0.5 mol. mp 67-68 (lit: 68-69)"
you put alpha-methyl-trans-cinnamic acid in, you get 2-methyl-3-phenyl-oxirane-2-carboxylic acid out...
--PSY420-- |
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joe_aldehyde
huxleys associate
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5653.90 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 9:43 pm |
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the page i am looking for <From benzaldehyde, sodium propionate and AcOH (200°C):
Chem. Ber. 16 (1883) 1437> isn't on the server, vitus... |
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PSY420
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| Joined: 30 Jun 2005 |
| Posts: 30 |
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1174.16 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 10:19 pm |
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It is there, but the experimental details concerning the reaction in question are rather sparse :
Chem. Ber. , 16; 1437 (1883)
A mixture of benzaldehyde, sodium propionate and glacial acetic acid heated to 180 - 200°C gives rich quantities of alpha-methyl-cinnamic acid next to a small amount of cinnamic acid.
--PSY420-- |
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Vitus
Psychoscientist
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| Joined: 19 Apr 2005 |
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2608.18 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 10:23 pm |
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yes it is I just looked at it..
under Chimie choose 'Berichte der Deutschen chemischen Gesellschaft zu Berlin'
Then choose '1883 . Jan.-Juni (Jg. 16)'
Then in the box Aller page type in 1437
et voilà.. |
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Vitus
Psychoscientist
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| Joined: 19 Apr 2005 |
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| Location: Dunwich |
2608.18 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 10:27 pm |
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A mixture of benzaldehyde, sodium propionate and glacial acetic acid heated to 180 - 200°C gives rich quantities of alpha-methyl-cinnamic acid next to a small amount of cinnamic acid.
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I guess that it has to be heated under autogenous pressure, considering the bp of benzaldehyde and GAA ? |
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PSY420
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| Joined: 30 Jun 2005 |
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1174.16 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 11:02 pm |
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DE2449928 can safely be regarded as unusable. They mix benzaldehyde with sodium ethanolate and alpha-(diethylphosphono)propionicacid methyl ester, which is made from alpha-bromopropanoic acid methyl ester and P(OMe)3. For everyone who still wants to read it: it's in example #8.
In J. Org. Chem., 18;1253 - 1257 (1953) propionic anhydride and Na propionate are used on 2,5-dimethoxybenzaldehyde (150°C)
--PSY420-- |
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joe_aldehyde
huxleys associate
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5653.90 Points
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Re: re: yet another neat way from BA to P2P
Fri Jul 01, 2005 11:07 pm |
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| PSY420 wrote: |
It is there, but the experimental details concerning the reaction in question are rather sparse :
Chem. Ber. , 16; 1437 (1883)
A mixture of benzaldehyde, sodium propionate and glacial acetic acid heated to 180 - 200°C gives rich quantities of alpha-methyl-cinnamic acid next to a small amount of cinnamic acid.
--PSY420--
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seems like quite a large number of members can read german true, though - the experimental details aren't too exhaustive.
and the price for alpha-methylcinnamic acid is just too high, i'd rather make EtNO2... |
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Vitus
Psychoscientist
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| Joined: 19 Apr 2005 |
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| Location: Dunwich |
2608.18 Points
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re: yet another neat way from BA to P2P
Fri Jul 01, 2005 11:24 pm |
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Shouldn't be that hard I guess, if they could perform it in 1883 why would it be a problem now?
Maybe the J.Chem.Soc. article of the same year has some more details. |
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