03-24-02 14:08
No 287299
I don't think there is any immediate need for the translation of JP44-009892, as it isn't a really preferable method - bromine and alpha-methylstyrene giving a 50:50 mixture of P2P and 2-phenylpropionaldehyde (which in turn are inseparable by distilling). Chem. Abs. 71, 61016x (1969) found in Post 243048 (Rhodium: "P2P from alpha-methylstyrene", Novel Discourse) is enough for anyone venturing into that synthesis.
Yes, please post the translation of JP44-010776 you gave me. I was saving it for a Master FAQ on all known synthetic routes to MDP2P, but with my current productivity rate, you better post them in this forum (in a separate thread), preferably with a little commentary on its origin from ../rhodium /tcboe/c
(Stranger)
08-27-02 10:16
No 349568
(Rated as: excellent)
Greetings from Room 101; it's good to see this forum still exists after these several years.
There was a character in the 2nd part I couldn't find, marked by ?.
--------
Experimental from Yakugaku Zasshi 77, 310 (1957):
1-(2-Methoxyphenyl)-2-propanone(II) Into 52g anethole dissolved in 400cc glacial acetic acid was added little by little while stirring 200g Pb3O4. During this time the warmth of the liquid was held to 40 degrees requiring approximately 2 hours. After the addition was complete stirring was continued for a further 1 hour at 40 degrees.
Next, a small quantity of water was added so that the excess Pb(OAc)4 dissolved, and the large portion of acetic acid removed under vacuum, then the remaining residual sediment extracted with ether. When nothing further could be extracted into the ether solvent, the residual sediment with 500cc of 20% sulfuric acid was boiled up for 3 hours with strong stirring. Cooled resultant's upper layer of oil was extracted with ether. Dried with calcium chloride, distilled, slightly yellow clear liquid, bp(14) 125-130 degrees. Yield 24g (42%). Semicarbazone: mp 157-159°C. In addition, a mixture of this semicarbazone with that previously yielded by Heinzelman's process melted without melting point depression.
N,alpha-Dimethyl-2-methoxyphenethylamine
Hydrochloride: white granular crystals (recrystallized from isopropanol, acetone 1:5 mixture) mp 129-130 degrees. In addition, a mixture of this product with that previously yielded by the technique of both Woodruff and Heinzelman melted without melting point depression.
--------
BTW if anyone wants to look for that mystery kanji character, it was a two-radical character, on the left rad85(water) and on the right rad63(door). The only refs I found to it were as a variant of another kanji which was only used in a place name for a river in China.
--------
DISCLAIMER: This translator's knowledge of Japanese is mainly focused on language useful in picking up and fucking japanese girls. As aforementioned translator has not to date been greatly successful in picking up and fucking aforementioned japanese girls, one may rightly deduce that the overall quality of the aforementioned translator's Japanese skills are still not fantastic. Although the attempt was made in good faith to accurately convey the contents of the original document, the aforementioned translator cannot be held responsible for any use or misuse of aforementioned translation due to aforementioned error in aforementioned translation (aforementioned).
(Stranger)
10-10-02 09:21
No 366771
(Rated as: excellent)
Patent JP-H07-149750 - From bromobenzene to P2P (../rhodium/archive/jp-h07-1
<0048> With commercial 2-bromotoluene(10.7g, 63mmol), magnesium ribbon(2.25g, 94mmol), and diethyl ether(60mL), a 2-methylphenylmagnesium bromide-diethyl ether solution was prepared via the usual method; under argon gas stream, and cooled to -78 degrees C, propylene oxide(8.75mL, 7.25g, 13mmol) was slowly dripped into this. With continuous stirring, the reaction liquid temperature was allowed to raise over 1.5 hours to room temperature. After, saturated aqueous ammonium chloride solution was added to stop the reaction, and it was poured into water(300mL); this was then extracted with diethyl ether(200mL x3). After this was done, the organic layer was washed with saturated aqueous sodium chloride(300mL), and dried over anhydrous sodium sulfate, using a water bath regulated so as not to exceed 25 degrees C. Crude 1-(2-methylphenyl)propan-2-ol was obtained by concentration under vaccum. A solution of this was made by dilution with acetone(300mL), then ice-cold Jones Reagent(2.67M, 23.4mL, 63mmol) was dripped in over 10 minutes; the solution was kept at this temperature for a further 30 minutes with periodic stirring. Next, 2-propanol(5.0mL) was added to eliminate excess reagent, and after a minute, neutralized with sodium bicarbonate, then the reaction liquid suction filtered through celite so any solids are really removed. The filtered liquid was then concentrated under vacuum using a water bath regulated so as not to exceed 25 degrees C, then again diluted with diethyl ether(300mL). This was washed in turn with water(300mL), then saturated aqueous sodium chloride(300mL), further dried with anhydrous sodium sulfate, then concentrated under vacuum using a water bath regulated so as not to exceed 25 degrees C. Residue was purified using silica gel column chromatography. The collected fraction, eluted in diethyl ether-hexane(10:90), was then concentrated under vacuum using a water bath regulated so as not to exceed 25 degrees C, and (2-methylphenyl)propan-2-one thereby obtained in the form of an oily material (5.50g, 59%).
<0049> IR(film): 3020, 2920, 1710, 1490, 1460, 1350, 1220, 1150, 740cm^(-11). H-NMR(200MHz in CDCl3): delta 2.14(3H,s,C3CH3), 2.25(3H,s,ArCH3), 3.71(2H,s,C1H2), 7.08-7.23(4H,aromatic ring proton). EIMS (relative strength %): 148(40,M+), 105(100,M-MeCO+), 43(62,MeCO+). EI-HIMS:(C10H12O) calculated value 148.0888 actual value m/z 148.0865 <0050> reference example 9 <0051>
-----------
Usual caveats about translator skill (or lack thereof) apply. In particular, the part where the sat. ammonia is added may be after the reaction stops rather than to stop the reaction, not exactly sure. Also it could be the entire system is 'ice-cold' for the Jones reagent addition, rather than just the JR. My apologies to the Japanese for my continuing massacre of their exquisite language.
(Stranger)
11-14-02 07:14
No 379539
Post 345932 (zara: "Ðåàëüíûå ñèíòåçû !", Russian HyperLab)Post 346626 (zara: "È åùå ñèíòåçîâ !", Russian HyperLab)
Heres a few good posts in the hyperlab that perhaps some bees would like to take a look at. The online translators ive used turn up lots of confusing points in russian text.
Thanks
(Newbee)
12-26-02 02:20
No 392850
http://l2.espacenet.com/dips/viewer?PN=J
or
../rhodium/projects/translat
Thank you!
(Newbee)
01-17-03 00:57
No 398865
They are two ref in german I would like to known in english; first is about chloroethyl BQ intermediate and second is about 5-oh indol synthesis from a common intermediate with this road
First: (liebigs ann chem bd 763 p 145)
2-(1-chlor-äthyl)-1,4-benzochinon(26) - Zu einer Lösung von 2.16 g (20 mMol) Benzochinon und 4.32 g (40.'mMol) alpha-Chlor-propionsaure in 40 ml Wasser und 20 ml CCl4 wurden bei 50-53° unter kräftigem Rühren gleichzeitig innerhalb 20 Min. 5 g (22 mMol) Ammoniumperoxydisulfat in 2o ml. Wasser und 3.4 g (20 mMol) Silbernitrat in 20ml Wasser gegeben. Nach weiterem 5 min. Rühren wurden noch 100 ml CCI4 zugefügt. DIe Phasen wurden getrennt und die wässrige Phase mit 50 ml CCI4 extrahiert. Die vereinigten organischen Phasen wurden mjt einer Aufschlämmung von 20 g Calciumcarbonat in 100 ml Wasser gewaschen. Nach Filtrieren, Trennen der Phasen, Trocknen (MgSO4) und Eindampfen wurden 2,14 g eines Produkts erhalten. das laut NMR-Analyse etwa 1.53 g (45 %) 26 und 0.61 g nicht umgesetztes Benzochinon enthielt. Das Benzochinon wurde bei 20°/0.5 Torr durch Sublimation entfernt und der Rückstand bei 50-60°/0.5 Torr destilliert. 26 bildet gelbe Kristalle vom Schmp. 54-56°, reagiert mit Wasser sowie Alkohol und ist lichtempfindlich. Es ist deshalb..... (dont have the next paper)
second: (ref unknown)
5-hydroxy-6-methyl-indol(9a)
Das Amin 3a (2-(2,5-dibenzyloxy-4-methyl-phenyl)-eth
AAV 4:
Hydrierung: Der Benzylether wird in THF gelöst und mit Pd/C (10%) versetzt. Es wird bei RT und 1-4 atm. in einer Wasserstoffatmosphäre bis zur Beendigung der H2-Aufnahme geschüttelt. Das nach der Aufarbeitung unter Argon zurückbleibende Öl wird mit Ether zur Kristallisation gebracht.
AAV 5:
Oxidation: Unter Argon werden 0.01 mol des Hydrochinon-Derivates in Aceton gelöst, mit 0.0001 mol DDQ versetzt und 24h bei RT unter Ar gerührt. Das Lösungsmittel wird abgezogen und der Rückstand mit Petrolether/Ether behandelt.
thank you german speaking bees!
(Master Searcher)
01-17-03 02:40
No 398890
quinone route German articles
German isn't my natural language so maybe someone can check it (Osmium?) (for Post 398865 (Chimimanie: "quinone road german articles", Novel Discourse) )
First one:
Liebig's Annalen Der Chemie bd (band?) 763 p 145
2-(1-chloro-ethyl)-1,4-benzoquinone (26) - To a solution of 2.16 g (20 mMol) benzoquinone and 4.32 g (40 mMol?) alpha-chloro-propionic acid in 40 ml water and 20 ml CCl4 at 50-53° under vigorous (strong) stirring within 20 minutes 5 g. (22 mMol) ammonium peroxydisulfate (bisulfate?) in 20 ml water and 3.4 g. (20 mMol) silver nitrate were added simultaneously. After stirring another 5 minutes 100 ml CCl4 was then added. The phases were seperated and the aqueous phase was extracted with CCl4. The combined organic phases were washed with a suspension of 20 g calcium carbonate in 100 ml water. After filtering, separation of the phases, drying (MgSO4) and evaporation 2.14 g of the product was obtained. The results of NMR analysis showed that it contained about 1.53 g (45%) 26 and 0.61 g unreacted benzoquinone. The benzoquinone was removed at 20°/0.5 Torr by sublimation and the residue was distilled at 50-60°/0.5 Torr. 26 forms yellow crystals with a melting point of 54-56°, reacts with water, somewhat with alcohol and is photosensitive. It is therefore....
second: (ref unknown)
5-hydroxy-6-methyl-indol(9a)
The amine 3a (2-(2,5-dibenzyloxy-4-methyl-phenyl)-eth
AAV 4:
Hydrogenation: The benzyl ether was dissolved in THF and spiked with Pd/C (10%). It was shaken at RT and 1-4 atm. in a hydrogen atmosphere until H2 uptake ceases. Then after the workup under argon the oil was crystalized with ether.
AAV 5:
Oxidation: Under argon 0.01 mol of hydroquinone derivative was dissolved in acetone, with 0.0004 mol DDQ added and stirred 24h (?) at RT under Ar. The solvent medium was drawn off and the residue was treated with petroleum ether/ether.
Edit: "DDQ amount conflict" /mindlib
http://www.geocities.com/dritte123/PSPF.
The hardest thing to explain is the obvious
(Chief Bee)
01-19-03 20:33
No 399740
"Relative affinity of tolyl and piperonyl radicals by direct but indirect comparison with various substituted aryl radicals"
Very boring and uninspiring title, and this also in French. But - this is one of the pioneer research papers regarding the peracid oxidation of isosafrole, where isosafrole glycol, its esters, isosafrole epoxide and MDP2P is discussed in-depth, covering almost 16 pages! The only thing that needs to be done now is to translate it to a readable language...
Bull. Soc. Chim. Fr. [4] 49,1738-53 (1931) (../rhodium/djvu /tiffenau.dj
Also, there is ../rhodium/pdf /benzodioxole.
(Chief Bee)
03-09-03 19:19
No 415062
The articles on L-Phenyl acetyl carbinol (L-PAC) below has been requested by GC_MS and retrieved/scanned by Uemura, they are however still in German, and Antoncho has expressed a wish to have the important experimental parts translated either to English or Russian:
Biochemische Zeitschrift 115, pp 282 (1921) (../rhodium/pdf /l-pac.neuber
Biochemische Zeitschrift 128, pp 610 (1922) (../rhodium/pdf /l-pac.neuber
Another gernam article in need of translation can be found in Post 411744 (Rhodium: "New P2P syntheses from industrial chemicals", Novel Discourse)
(Chief Bee)
03-10-03 00:54
No 415195
The following articles on chemical manipulations of safrole and related compounds would be very nice if someone could translate into english.
../rhodium/projects/translat
../rhodium/projects/translat
Browser plugin to read *.djvu files: http://www.lizardtech.com/download/
(Chief Bee)
03-27-03 01:56
No 421565
Synthesis of 3,4-methylenedioxyphenyl-2-propanone
Jingxi Huagong, 18(6), 321-324 (2001) (../rhodium/projects/transla
Abstract
A process for the prepn. of (3,4-methylenedioxyphenyl)-2-propanone was studied by means of epoxidn. of safrole and subsequent catalytic isomerization of the so-obtained epoxide. (3,4-Methylenedioxyphenyl)-2-propanone is a useful intermediate for the synthesis of methyldopa, an important antihypertensive agent. The optimal result was obtained by expts. done under various conditions, such as kind of catalyst, consumption of catalyst and reaction time.
The yield of epoxidn. achieved 92% at n(catalyst):n(safrole) = 0.0039, n(catalyst):n(H2O2) = 0.0046, n(H2O2):n(safrole) = 0.87, reaction time 4 h, reaction temp. 356-358K and with 1,2-dichloroethane as solvent. The yield of isomerization achieved 91% at n(LiI):n(crude product) = 0.045, reaction time 6 h, reaction temp. 351-353 K, with Et acetate as solvent and LiI as catalyst. Purity of the title compd. was over 95%.
____ ___ __ _
Preparation And Some Reactions Of 2,5-Dibromobenzaldehyde
J. Nanjing Univ. 27(1), 191-194 (1991) (../rhodium/projects/transla
Abstract
Bromination of benzaldehyde with Br2 in HOAc in the presence of FeCl3 gave 60-70% 2,5-dibromobenzaldehyde (1), which was converted to ethyleneacetal (2) and then treated with CH3ONa in DMF containing Cul to give 2,5-dimethoxybenzaldehyde (3) or 2-Methoxy-5-Bromobenzaldehyde (7) according to the reaction conditions. Oxidation of compounds 1, 3, and 7 with H2O2/NaOH produced the corresponding carboxylic acids. The structures have also been confirmed by IR, NMR, and mass spectral data.
____ ___ __ _
Improved synthesis of 3,4,5-trimethoxy-benzaldehyde
Chemical Reagents/Huaxue Shiji 21(1), 50 (1999) (../rhodium/pdf /345-tmba.hua
(Chief Bee)
04-03-03 03:08
No 423458
1-Phenyl-2-Propanones from 1-Phenyl-1-Hydroxy-2-Propanones (../rhodium/projects/transla
Abstract
1-Phenyl-2-alkanones I (R = C1-4 alkyl; R1, R2 = H, OH, halo, NH2, C1-4 alkyl, C1-4 alkoxy; R1 and R2 may form a 5- to 7-membered ring contg. 1-2 O atoms), useful as intermediates for pharmaceuticals and agrochem., were prepd. by reducing 1-hydroxy-1-phenyl-2-alkanones II. Thus, heating 0.10 mol II (R = Me; R1 = 4-OH; R2 = H), 120 mL 5 N HCl, and 25 g powd. Sn 24 h at 80° gave 93 mol% I (R = Me, R1 = 4-OH, R2 = H).
____ ___ __ _
This one is also in japanese: Post 451720 (Rhodium: "Isosafrole to MDP2P by auto-oxidation!", Novel Discourse)
(Master Searcher)
05-23-03 05:43
No 434879
Can someone translate this into English?
1> 3 Zhurnal
2. 2 Zhurnal analiticheskoi khimii
3. 1 Zhurnal epidemiologii i mikrobiologii
4. 1 Zhurnal evoliutsionnoi biokhimii i fiziologii.
5. 1 Zhurnal evoliutsionnoi biokhimii i fiziologii
6. 1 Zhurnal Evrofish
7. 1 Zhurnal. Fizicheskii otdiel
8. 2 Zhurnal fizicheskoi khimii
9. 1 Zhurnal khimicheskoi promyshlennosti
10. 2 Zhurnal mikrobiologii, epidemiologii i immunobiologii
11. 1 Zhurnal mikrobiologii, fatalogii i infektsionnykh boleznei
12. 1 Zhurnal neorganicheskoi khimii
13. 1 Zhurnal obshchei biologii
14. 2 Zhurnal obshchei khimii
15. 1 Zhurnal organicheskoi khimii
1. 2 Zhurnal organicheskoi khimii
2.+ 2 Zhurnal organicheskoi khimii.
3.# 2 Zhurnal organicheskoi khimii. English
4. 1 Zhurnal organicheskoi khimii. English. Journal of organic
chemistry of the USSR
5. 1 Zhurnal organicheskoi khimii. English. Russian journal of
organic chemistry
6. 1 Zhurnal po sel'skokhoziaistvennym naukam
7. 1 Zhurnal prikladnoi khimii
8.+ 1 Zhurnal prikladnoi khimii (Leningrad, R.S.F.S.R.)
9. 2 Zhurnal prikladnoi khimii (Leningrad, R.S.F.S.R.)
10.# 1 Zhurnal prikladnoi khimii (Leningrad, R.S.F.S.R.) English.
11. 1 Zhurnal prikladnoi khimii (Leningrad, R.S.F.S.R.). English.
Russian journal of applied chemistry
1. 1 Zhurnal prikladnoi mekhaniki i tekhnicheskoi fiziki
2. 1 Zhurnal prikladnoi spektroskopii
3. 1 Zhurnal Russkago fiziko-khimicheskago obshchestva
4. 3 Zhurnal strukturnoi khimii
5. 1 Zhurnal Vsesoiuznogo khimicheskogo obshchestva im. D. I.
Mendeleeva
6.# 1 Zhurnal Vsesoiuznogo khimicheskogo obshchestva im. D.I.
Mendeleeva.
7. 1 Zhurnalnaia forma schetovodstva v sovkhozakh
8. 1 Zhurnal'no-ordernaia forma ucheta na predpriiatiiakh lesnogo
khoziaistva / A. N. Edoshin. -
9. 1 Zhurnalno-ordernaia forma ucheta v kolkhozakh.
10. 1 Zhurnaly i doklady Sovieshchaniia po organizatsii
Ekaterinoslavskoi oblastnoi sel.-khoz. opytnoi stantsii,
sozvannage Ekaterinoslavskoi gubernskoi zemskoi upravoi
http://www.geocities.com/dritte123/PSPF.
http://forum.faithfreedom.org
(HyperLab Bee)
05-23-03 09:01
No 434908
1. Zhurnal = Journal
2. Zhurnal analiticheskoi khimii = Journal of analytical chemistry
3. Zhurnal epidemiologii i mikrobiologii = Journal of epidemiology and microbiology
4. Zhurnal evoliutsionnoi biokhimii i fiziologii = Journal of evolutional biochemistry and physiology.
5. Zhurnal fizicheskoi khimii = Journal of physical chemistry.
6.Zhurnal khimicheskoi promyshlennosti = Journal of chemical industry.
7. Zhurnal neorganicheskoi khimii = Journal of inorganic chemistry.
8. Zhurnal obshchei biologii = Journal of general biology.
9. Zhurnal obshchei khimii = Journal of general chemistry.
10. Zhurnal organicheskoi khimii = Journal of organic chemistry.
11. Zhurnal prikladnoi khimii = Journal of applied chemistry.
12. Zhurnal prikladnoi spektroskopii = Journal of applied spectroscopy.
13. Zhurnal Russkago fiziko-khimicheskago obshchestva = Journal of Russian physical and chemical society.
(Master Searcher)
05-23-03 16:28
No 434965
Thanks, murmur. The Journal of Physical Chemistry (USSR) 24, 745-59 (1950) has the 'Electrochemical reduction of nitromethane to methylamine performed in aqueous HCl' article in it. There's a gap in a couple of years (1949-1953) around that time at one library (WWII/cold war?). At another library there is a gap in the 1940's - 1950's in the Journal of General Chemistry USSR, but I found the article I was looking for at the first library. I'll see if I can find J. Phys. Chem. USSR somewhere else.
Edit: If you need this article, you can see it here: http://chemister.da.ru/Books/Chembooks/Z
http://www.geocities.com/dritte123/PSPF.
http://forum.faithfreedom.org
(Hive Bee)
07-10-03 22:00
No 446249
(Rated as: excellent)
Biochemische Zeitschrift 128, pp 610 (1922)
....
....
A. Further statements about the bio-synthesis figure of l-Phenyl-acetyl-carbinol, C6H5*CHOH*CO*CH3
1,25 kg starchsyrup, which can serve as a cheap raw material, was solved in water; under addition of 1 kg barm Senst was then a volume of 25 l produced. After 1/2 hour fermentation, 100 g Benzaldehyd was added under stirring in small portions. After 3-day fermentation by room temperature, which was supported through often shaking, the barm was filtrated out over Kieselgur(ml:celite) and the filtrate (23,6 l) was ether-ed out in the style, Neuberg and Hirsch (115,282. 1919) described. The ether solution was cramped to a small volume, dried with annealed sodiumsulfate and then total liberated from the ether, which left a residuum of 91 g. It was absorbed with approx. 1/2 l ether and, for the removal of acid, shaken fast 2-times with each 100 ccm saturated soda solution, then shaken with the same amount of water. The united watery parts were ether-ed out once again and these extracts were given back to the mainamount. The achieved watery liquid is called acidfraction; there refurbishment will be described later in this report.
The, from acids liberated, etherlayer was shaken out 5-6 times each a 1/2 hour with each 200 ccm of a approx. 25% Sodiumbisulfitesolution. Also after this treatment had a probe of the ether residuum, from which was also SO2 removed, small amounts of Phenyl-brenztrauben-alkohol; because she reduced Fehlingsche mixture, but only in the boiling heat. A total quantitative seperation of the Ketol from the Benzylalkohol was not achieved through Sodiumbisulfite. To seperate the carry-along-Benzylalkohol-carry-over, the Sodiumbisulfitezone was shaken out once with ether, whereby they though given off a small amount Ketol again.
This ether portion wasn´t poured back to the stock solution, but finished off itself. In the following she is called intermediate fraction.
The losses of Ketonalkohol through the described treatment were balanced through the fact, that the recovered product from the Bisulfit-connection is very clean.
The last remaining ethersolution contained only the Benzylalkoholfraction and a small amount of high-boiling connections of indifferent characters.
c) Ketonalkoholfraction
The Sodiumbisulfitesolution was treaten at common temperature with solid Sodiumbicarbonat, so long, until the evolution of Kohlendioxyd stopped, (approx. 300 g was used).
Then it was shaken out immediately 5 times with ether, we united the ether extracts, dried over Glaubersalz and got after evaporation of the ether 21,5 g of a green-yellow oil.
The pressure of the vacuum-destillation was, through the bad caoutchouc material, not absolute constant.
Following fractions were caught: (see table I)
b) Benzylalkoholfraction
During the evaporating of the, cleaned and dried over Na2SOx like described before, ether solution remained a residuum of 45 g. This provided through a vacuum destillation following fractions: (see p612 above)
The fractions 1-3 didn´t reduce alkaline copper solution and were predominantly Benzylalkohol. Fraction 4 contained the rests of the Ketol, whilst the residuum comprised not nearer defined, in part higher molekular products, which weren´t seperated through destillation yet; maybe they are containing Methyl-phenyl-glykol. Those unknown part went over under 11 mm pressure mainly between 190-225° .
a) acidfraction
(ml: They got 2,4 g Benzoeacid, and 2 g of a residuum.)
No responsibility for translation faults; only for theory!!
(Hive Bee)
07-18-03 16:53
No 448282
pp282 (1921)
--------------------------
Experimental Part
I. The retrieval of the Carboligase-effect
To a preparation of 280 g cane sugar and 280 g top-fermented barm (Senst) in 7 l water was added after the on-fermentation 25 ccm fresh destilled benzoeacid-free Benzaldehyd. The batch, which was left at room temperature, had at the next day only traces of smell of bitter almond oil. After addition of more 15 ccm Benzaldehyd, the fermentation-stuff stood 48 hours, until the evolution of Kohlensäure stopped and the smell of Benzaldehyd was away.
...
...
For the isolation is the extraction with ether practical, because it´s so possible, to extract through 3-4 times-removing the reducing substance almost completely from the fermentation stuff. 3 l of it was shaken so often with ether, until the residuum Fehlingsche Mixture also with digestion didn´t reduce. After seperation of the ether on the water-bath remained a bright-yellow oil, which had beside the characteristic smell of Benzaldehyd a prickley smell. The oil was´nt soluble in water(nearly nothing), in organic solvents easy soluble (with exception of petrolether and Ligroin), ....
II. The chemical nature of the, through the Carboligase, synthesized connection
a) .....
..... New material was produced this time with a under-fermented barm-race.
The fermentation stuff contained 300 g Rohrzucker and 300 g barm (under-fermented beerbarm from the Berlin Institute for fermentation industry) in 7,5 l water. After occured on-fermentation was 30 ccm fresh-fractionated Benzaldehyd added and the mixture left 3 days at room temperature. We noticed the end of the fermentation now, as in the later Saccharose-experiments, through the negative outage of the Fehlingsche reaction in a pattern, which was before 4 times extracted with ether. ........
b)......
The next experiments were aimed at the figure (so clean as possible) of the, through their Phenylhydrazon-known, substance.
To a solution of 600 g cane sugar in 15 l water was added 600g barm Senst and at once 60 ccm Benzaldehyd. After 3- day storage at room temperature was a quantum of 12,5 l filtrated fermentation-stuff extracted exhaustive with ether, the solvent after drying over annealed Glaubersalz (ml:sodium sulfate *"H20") chased away on the water-bath, and the residuum destilled with vacuum. By 15 mm went- far above of the boiling point of benzaldehyd- between 102-156° a oily liquid over. Withal repeated rectifications wasn´t it possible to isolate, within narrow temperature ranges, volatilised uniformly fractions. .............
Better results got later Mr.Dr. Ohle with the, over the bisulfite-connection cleaned, substance, which is currently busy with more analysis.
....
The connection is soluble in alcohol, ether, Benzol, Toluol, Chloroform, Schwefelwasserstoff and Essigester, not or only very less in petrolether and Ligroin.
c) ....
600 g barm (Senst) was suspend (ml: third form??) in 15l water, which contained 600 g solved cane sugar. After the Kohlensäure evolution had begun, we did 60 g pure Benzaldehyd in, digested 4 days at room temperature and more 24 hours at 37° until the complete usage of the sugar happened. 11 l of the clear-filtrated mash was shaken with ether out, the extracts liberated through evaporation of the solvent and destilled under reduced pressure. Under 16-17 mm went over: (ml:see table p298)
f) .....
The base material was produced, like descriped often before, through the fermentation of 1 kg Saccharose in 25 l water with 1 kg Patzendorfer under-barm in presence of 100 g Benzaldehyd. From the filtrated fermentation-stuff was 23 l processed, the residuum of the ether-extract was seperated in the following parts: (ml: see p301)
III. Inquests about the biochemical behavior of the Carboligase
a) ....
(ml: They found the Carboligase in all barm species, they used; in top-fermented barm, in under-fermented races and also in dried-compounds)
b) ....
The fermentation-stuff contained 1200g starchsirup 1)(1: We used it instead of pure grape-sugar, because of its cheaper price.) and 1 kg barm Engelhardt in a total volume of 25 l. After the Kohlendioxydevolution occured, 80 ccm Benzaldehyd was added. After 3-day standing at room temperature, the fermentation was complete.
...
21,4 l filtrate was ether-ed out and rektifiziert after the evaporation of the ether.
(ml: see fractions I-V at page 303)
Portion I and II reduced Fehlingsche Solution in the heat, whilst the other portions reduced already in the cold.
The optical inquests of the three highest fractions (each 0,10 g in 5 ccm alcohol solved) showed in the 1-dcm-tube following values: (ml: see frations III-V page 303)
c) ....
(ml: in the experiments a and beta, they used sap, produced from dry-barm)
a) With exception of the first fraction, which smelled like Benzaldehyd, all fractions gave a positive Fehlingsche reaction in the cold. The optical inquests showed for fractions II-IV (each 1,0 ccm in 5,0 ccm abs. alcohol solved) no deflection. 1,0 ccm of the fraction V, in 5,0 ccm abs. alcohol solved, rotated in the same circumstances to the left, = -1,0° .
...
Whereon the creation of a inactive condensation-product during the cells-free fermenation in contrast to the creation of a active form during the fermentation with living barm is caused by, we cannot say. Maybe comes a Pseudomerisierung to the Dioxy-propenyl-benzol:
C6H5*CO*CHOH*CH3---------C6H5*C(OH):C(OH
which complies to the Enolcreation of the Ketozucker or to the relationships between Glycolaldehyd-dicarbonacid and Dioxy-maleinacid, into consideration.
beta) (ml: see fractions page 306)
The assay with Fehlingscher mixture gave for portion I
a positive reaction during boiling, whilst the other fractions reduced already in the cold. All parts were optical effectless.
d) Experiments about the alliance of Acetaldehyd and Benzaldehyd without coeval-proceeded fermentation.
alpha) ....
At 120-135° and 15 mm pressure went only a few drops of a yellow oil over, which didn´t reduce Fehlingsche solution and were optical inactive.
beta) (ml: see fractions at page 307)
The last portion congealed in parts to a crystal-mush and reduced Fehlingsche solution not until heating; the first was mostly Benzoeacid. As a result of the low yield of the reducing substance wasn´t it possible to produce a derivative of the Ketonalcohol.
e)...
alpha) 200g barm (Engelhardt) was allocated in 10 l water and to this was added 25 g fresh-fractionated Brenztraubenacid. The mixture was digested at 37° . After 24 hours it was possible to see the Carboligase-effect in the occuring of a optical activity. The filtrated fermentation-stuff showed in the 2-dcm-tube -0,4° .
We added again, because the smell of the bitter almond oil was nearly disappeared, 10 ccm Benzaldehyd. After 48 hours we added 100 g Barm and 8,0 g Brenztraubenacid. At the next day the rotation in the 2-dcm-tube was -0,75° . When after 6 days the CO2 evolution ended, we filtered, and ether-ed out 9300 ccm. (ml:13-14 mm pressure, see fractions page 308)
beta) In a other experiment the fermentation-stuff contained 25 g Brenztraubenacid and 20 g barm (Senst) in a total volume of 10 l . After the on-fermentation was added 20 ccm Benzaldehyd, and after more 6 hours 5ccm. After 3 days at 37° the reaction had finished. 9480 ccm of the filtrated fermentation-stuff was ether-ed out and the residuum, which remained after the flash-off of the ether, was destilled at 11-12 mm. (ml: see fractions page309)
Soon in the nozzle crytals appeared, the destillation was aborted. Part I reduced Fehlingsche mixture in the heat, all other parts already in the cold.
No responsibility for translation faults!
(HyperLab Bee)
07-23-03 14:26
No 449248
(Rated as: excellent)
Novel method of synthesis of 2-(beta-aminopropyl)-1,4-dimetoxybenzene
Y.M. Yutylov, V.F. Malutina, L.I. Shcherbina, K.M. Krylova
Institute of phisical and organic chemistry and carbonchemistry, NAS of Ukraine, Donetsk.
Requsted by Chimimanie.
Experimental part.
The chromatographing of 2-(beta-oxypropyl)-1,4-dimetoxibenzene and 2-(beta-aminopropyl)-1,4-dimetoxibenzene
was executed on a gas chromatograph L.CH.M.-8M. The length of the column 1.5 m, the diameter 3mm;
The bearer - Chromaton N-AW (0.16 - 0.20 mm ), containing 5% of XE-60 phase; Temperature of the thermostat 200 C,
temperature of the evaporator - 250; gas-bearer - helium.
2-(beta-oxypropyl)-1,4-dimetoxibenzene (V).
A) Into 0.25 L flask , equipped with a low-temperature thermometer, stirrer, drop funnel, backflow condenser,tube for the introduction of dry nitrogen (the speed of one was controled by a sweet counter, connected to the backflowcondenser exit), 10 ml of the absolute ether were placed. When the flask was flushed by nitrogen, 1.4 g. of well cuted lithium were added, with constant flow of nitrogen. Lithium had a form of a plate with a square 1 sm^2, and thickness 1-2mm. The temperature was reduced to -15 C. During constant stirring, 10.3 ml (9.16 g., 0,2 mol) of a dry n.-butylchloride were added from the drop funnel at temperature (-15)-(-10) C. The reaction mass was holded at 0 C during 2 hr., and then temperature was rised to 20 C (it rises by itself) and a solution of 10.35 g. (0.075 mol) 1,4-dimetoxibenzene [13] in 40 ml of absolute ether was added in one portion. The mixture was stirred during 1 hr., and left for a night. 10 ml (8.59 g, 0.15 mol) of a dry alpha-propyleneoxide at 0 C were added dropwise to the reaction mixture at 0 C the next day during 1 hr., and the mixture was stirred
during 3 hr., and left for a nihgt. The content of the flask was poured out into 150 ml of cooled water. The layer of ether was separated and water solution was extracted with 2x20 ml ether, united, dried over waterless Na2SO4, then the solvent was topped. The residue was distiled in vacuum and a fraction 159-161 C at 8 mmHg was gathered. 12.8 g. (87%) of 2-(beta-oxypropyl)-1,4-dimetoxibenzene of a high purity were obtained.
B) Butyllithium, which was received as described in the section A from 30g (4.28 mol) of lithium, 244 ml (217 g) of chlorous n.-butylchloride in 110ml of dry ether, was added, during intensive stirring at 0 C to a solution of 220(1.6 mol) g of dimethyl ether hydroquinone in 350 ml of dry m-xylol. (Volume of the flask = 2L) Reaction mass was holded during 1hr. with constant growth of temperature from 0 to 10 C, then temperature was raised to 20 C and the mass was holded during 16 hr. Then temperature was decreased to 0 C and 223 ml (191g, 3.3 mol) of dry propylenoxide were added by drops at intansive stirring. The mixture was heated to room temperature and holded for 16 hr. then it was poured out into water, water layer was separated and washed thrice by portions of 15s ml of m-xylol. The xylolic solutions were united with the main mass of xylol solution and dried over waterless Na2SO4 for 2-3 hr., then m-xylol and diethyl ether hydroquinone were distiled (130-132 C 8 mmHg.). The residue was distiled in vacuum 159-161 C at 8 Hgmm. Yield of spirit - 281.5g (90%).
C) 500 ml of dry m-xylol were added to 70g (10 mol) of fine cutted lithium in argon atmosphere in a 5 L three-neck-flask equiped with a stirrer, backflow condenser, drop funnel, a thermometer and a tube for a introduction of a gas. 570 ml (507.3 g 5.48 mol) of n-butylchloride were added by drops at an intensive stirring and temperature (-15 C) -(-10 C). After 2 hr. of stirring solution of 515g (3.73 mol) of dimethyl ether hydroquinone in 1000 ml of dry m-xylol was added to the mixture at 0 C, then stirring during 1 hr.
and then holding at room temperature 15-17 hr. Then the mixture was cooled to 0 C and 520 ml (446.68 g 7.7 mol) of dried over molecular sieves of 3A type propylenoxide (15g of sieve per 0.5 L) was added during 1.5-3.0 hr. After 3 hr. of stirring the mixture was holded at room temperature during 15-17hr. Then unreacted lithium was separated, reaction mass was washed by water, dried over 100 g. of waterless sodium sulfate, then m-xylol was topped and the product of the reaction was distiled in vacuum. boiling point 159-161 C at 8 mmHg .
Yield of spirit 475 g. (~65%).
D) 51.5g (0.37 mol) of dimethyl ether hydroquinone and 7 g. (1 mol) of fine cutted lithium were added to a solution of 100 ml of dry m-xylol in argon environment. (The mixture is in a 0.5 L round-bottom flask equipped with a low-temperature thermometer, stirrer, drop funnel, backflow condenser, tube for the introduction of a gas). The temperature reduced to -10 C. Then at constant stirring 10.3 ml (0.1 mol)of n-butylchloride was added by drops at temperature -10 C. Then the mixture was holded at the temperature during 2 hr., then temperature was enabled to raise spontaneously to room temp. and the mixture was holded during 15-17 hr. Then the reaction mass was cooled to 0 C, and 52 ml (0.75 mol) of dried over molecular sieves propylenoxide was added by drops during 1-1.5 hr. After 2 hr. of stirring the mixture was left at room temperature for 15-17 hr. Then unreacted lithium was separated, the reaction mass was washed by water, dried over 10 g. of waterless sodium sulfate, then m-xylol was topped and then unreacted 1,4-dimetoxybenzene and the product of the reaction was distilled in vacuum. Boiling point 159-161 C 8 mmHg . The yielfd of spirit 46 g. (63%).
2-(beta tosyloxipropyl)-1,4dimetoxybenzene (V|||).
982 g.(5 mol)of 2-(beta-oxypropyl)-1,4-dimetoxybenzene and 2.0 L.(24.7mol) of pyridine, dried over solid alkali were loaded in a 5 L. flask . The content of the flask cooled to 0 C and at intensive stirring 953 g. (5 mol )
of a fines n-toluenesulfochloride were added. Rise of temperature to 55 C was observed. The flask was closed up by a cork and putted to a refrigerator (+5 C) for 15 -20hr.
A residue of muriatic pyridine and a weak yellow color appeared. The reaction mixture was poured out into 10 L of water with ice. The reaction product was filtered, washed by water, by 5% solution of hydrochloric acid, again by water and by 0.1 L of methanol. Received 2-(beta tosyloxipropyl)-1,4-dimetoxybenzene was dried on air.
The yield of tosylat is 1647-1699 g. (94-97%). The boiling point 73.5-74.0 C.
The filtrate was acidified by a concentrated HCl (1 L), evaporated, the recidue was hardly alkalified by a Concentrated solution of NaOH, pyridine was separated, dried and distilled.
2-(beta-benzenesulfonyloxipropyl)-1,4 dimetoxibenzene (|X).
into 250 mL flask there were placed 39 g. (0.2 mol) 2-(beta-oxipropyl)-1,4dimetoxibenzene and 20 ml (0.24 mol)dried pyridine. The mixture was cooled to 0 C and to a stirred mixture 26 g. (0.2 mol) of benzenesulfochloride was added. The rxn was left standing for 20 hr. at 0-5 C. Then the rxn was poured into 300 ml of 10% solution of hydrochloric acid. The upper organic layer was separated and dried on air during 5 hr.
Yield – 65 g. (97.2%) Boiling point 44.5-46.0 C.
2-(beta-n-Nitrobenzenesulfonyloxypropyl)
The experiment was made similar to the receiving of tosylat (V|||) from 1.96 g. (0.01 mol) 2-(beta-oxypropyl)-1,4-dimetoxybenzene in 40 ml of pyridine and 4.4 g. (0.02 mol) n-nitrobenzenesulfochloride.
Yield of nitrobenzenesulfonate – 3.3 g. (87%). Purification – recrystallization from a spirit. Boiling point 97-98 C.
2-(beta-aminopropyl)-1,4- dimetoxybenzene (|)
A. Into 2.7L autoclave, (for work at 50 atm.) there were placed 350.5 g. (1 mol) of 2-(beta-tosyloxpropyl)-1,4-dimetoxybenze
Portions (2x250 ml) of weak hydrochloric acid (1:3). Amine was separated by adding to water-acid extract 20% solution of KOH until pH 9-10 wasn’t received. The oily layer, containing amine was separated and dissolve in benzene (200ml). The solution was dried for 5 hr. by solid alkali and after the distillation of the dissolvent, 2-(beta-aminopropyl)-1,4dimetoxibezene at 144-148 C 8 mmHg was distilled
Yield of amine 168-176 g. (86-90 %)
B) Ammonolysis of 2-(beta-n-nitrobenzenesulfonyloxipropyl)
C) Ammonolysis 2-(beta-benzenesulfonyloxipropyl)-1,4dim
Hare Krishna
(Hive Bee)
08-02-03 17:09
No 451248
PREPARATION OF N- SUBSTITUTED METHYLENE TRYPTOPHAN ESTER
PURPOSE:To obtain the titled compound which is an intermediate for tryptophan in high yiled under mild conditions, by reacting an N-(substituted methylene)glycine ester with a (3-indolylmethyl)trialkylammonium salt as raw materials.
CONSTITUTION:An N-(substituted methylene)glycine ester of formula I [R<1> and R<2> are H, alkyl, (un)substituted aryl or (non)cyclic thioketal residue; R<3> is ester residue] is reacted with a (3-indolylmethyl)trialkylammonium salt of formula II (R<4>, R<5> and R<6> are alkyl; X<-> is halide ion, sulfate ion, alkylsulfate ion, hydrogensulfate ion, hydroxyl ion, etc.) to give an N-(substituted methylene)tryptophan ester of formula III. The raw materials of formulas I and II are readily obtained in high yield. The reaction is preferably carried out in a homogeneous solvent and between two phases of solvents. The compound of formula III is hydrolyzed to afford tryptophan readily.
Patent JP56138171
A Dream Within A Dream (http://www.poedecoder.com/Qrisse/works/
(Stranger)
08-13-03 02:16
No 453204
Bulletin de la Société chimique de France
year: 1964 pages 2523-2532 'La décarboxylation thermique des acides alpha-aminés' part I
year: 1965 pages 929-933 'La décarboxylation thermique des acides alpha-aminés' part II
The decarboxylation of amino acids (including tryptophan).
Can someone copy these and have a French speaker translate them or just the important parts?
(Hive Bee)
08-13-03 21:45
No 453387
Can someone translate the 'Resultate und Diskussion.' and the experimental of that:
../rhodium/pdf /mescaline.4-s
Post 423427 (Rhodium: "Synthesis of Novel Mescaline Derivatives (German)", Novel Discourse)
I am especially interested in fluorinated mescalin analog
Thank!
(Chief Bee)
08-16-03 14:28
No 453903
Novel method for synthesis of 2-(b-aminopropyl)-1,4-dimethoxybenzene.
Zhurnal Prikladnoi Khimii (Sankt-Peterburg), 72(10), 1691-1696 (1999) (../rhodium/pdf /archive/25-d
Abstract originally posted in Post 426579 (Chimimanie: "ref on dimethoxy-alcohols", Russian HyperLab)
The full article originally posted in Post 428187 (Flogiston: "Fire in the hole!!!!!", Russian HyperLab) (DjVu format, last page has a minor data loss)
Edit: It seems like we have the experimental part already translated in Post 449248 (Flogiston: "Novel method of synthesis of 2-(beta-aminopropyl)-", Novel Discourse) (Thanks for noticing, Chimimanie, and thanks Flogiston for the translation - I honestly missed to read that post above last month).
Still, the first part of the article with results and discussion, it surely must contain interesting information unknown to western science. Can any russian speaker please look it over and summarize any interesting discussion about optimization, side reactions and references to related syntheses? There is no need for a word-to-word translation, I am just interested in taking part of any interesting information disclosed in the article.
(Stranger)
08-18-03 00:26
No 454192
Here's the articles mentioned in
Post 453204 (Herr_Ovalmeister: "Bulletin de la Société chimique de France...", Novel Discourse)
Can anyone translate these?
http://www.sciencemadness.org/scipics/La
http://www.sciencemadness.org/scipics/La
(Newbee)
08-22-03 04:39
No 454940
for
Post 453387 (Chimimanie: "German translation: mescalin analog", Novel Discourse)
Here are the first three paragraphs.
Results and Discussion -- In contrast to the earlier described method for the production of 2-(4-alkoxy-3,5-dimethoxyphenyl)-ethylam
Interestingly enough, both nitro-olefins 9a and 9b are produced as the (E) and the (Z) product ((E)/(Z) 57:43 and 45:55). In an entirely different synthesis the trans product is formed exclusively. Using 1H-NMR spectroscopy it can be shown that occasionally two products with the same "splitting up", although partly very different chemical displacement (shift?) were present. The GC/MS analysis showed that the product just from the mass passes (the test); the mass corresponds to 9b and 9c, respectively. The effect of the temperature and the achirality of the GC-column were not further investigated, therefore the sequential reaction provides the desired product.
The reduction to the phenylakylamines 10a-e and 12a-i takes place with AlH3, generated from LiAlH4 and H2SO4 in THF [8d], where its shown that its enough when 95-97% H2SO4 is used instead of 100% (from oleum and concentrated H2SO4). The yield as HCl salt is 49-81%.
(Hive Bee)
09-12-03 22:49
No 458736
Thank you for the translation, mister ovalmeister
for the decarboxylation article in french, which part are you interested most?
i have trouble with your pdf, but i own one of those article in my personal refs, and the other one i could fetch it at library soon. As far as i remember, the method use a ketone, like acetophenone, and they have got good yield for tryptophan, but not so good yield for alpha-methyl-phenylalanine, due to transamination reaction.
Ask me which part you are interested, for me i think the tryptophan one is good, and i will traduct you the relevant experimental if you are interested.
Chimimanie.
(Hive Bee)
09-23-03 17:36
No 460561
http://biq.iqm.unicamp.br/arquivos/teses
Edit: I noticed you had to register; the direct link for this thesis is: http://biq.iqm.unicamp.br/arquivos/teses
Autor: Kreutz, Olyr Celestino
Título: Síntese de a-oxo-o-metiloximas e Redução Enantiosseletiva com Fermento de Pão. Obtenção de Intermediários para a Preparação de 1,2-aminoálcoois Quirais
Ano: 1999
Orientador(a): Prof. Dr. Paulo José Samenho Moran
Departamento: Química Orgânica
Palavras-chave
Biotransformação, Baker's yeast, Saccharomyces cerevisiae
Resumo: Neste trabalho foram desenvolvidas metodologias de redução assimétrica de alfa-oxo oximas do tipo ArC(O)C(NOR)R, utilizando Fermento de Pão como agente de redução assimétrica. Sintetizou-se várias alfa-oxo oximas (64 a 96% de rendimento) com o objetivo de estudar a influência dos grupos Ar, R e R (Ar = Bn, Furil, Naftil, 3,4-metilenodioxifenil, R = R = H = alquil ou aril) na enantiosseletividade da redução da função cetônica pelo Fermento de Pão (Saccharomyces cerevisiae). Os resultados obtidos na redução enantiosseletiva destes compostos demonstram a grande aplicabilidade desta estratégia na síntese de 1,2-aminoálcoois opticamente ativos. Os álcoois obtidos (65-99% de excesso enantiomérico) podem ser intermediários para a preparação da norefedrina, norpseudoefedrina e análogos. Foi feito um estudo de Ressonância Magnética Nuclear para determinação da configuração (E/Z) da ligação C=N destas oximas. Para tanto, sintetizou-se os dois isômeros possíveis e, através da comparação dos respectivos espectros de RMN H e C foi possível estabelecer a configuração.
Abstract: In this work, methodologies for asymmetric reduction of alpha-oxo-oximes, ArC(O)C(NOR)R, had been developed using Baker's yeast as reduction agent. Several alpha-oxo oximes (64-96% yield) where synthesized in order to study the influence of the groups Ar, R and R (Ar = Bn, furyl, naphthyl, 3,4-mehtylenedioxyphenyl, R1 = R = H = alkyl or aryl) in the enantiosselectivity of the reduction of the keto function by Baker's yeast (Saccharomyces cerevisiae). The results of these enantioselective reductions indicate the great applicability of this strategy in the synthesis of optically active 1,2-aminoalcohols. The obtained alcohols (65-99% ee) are intermediates for the synthesis of norephedrine or norpseudoephedrine analogous. A Nuclear Magnetic Resonance study was made to estabilish the E/Z configurations of the C=N bond of those oximes. In such way, the two possible isomers where synthesized and, through the comparison of the NMR H and C spectra of these compounds it was possible to assign the respective E/Z configuration.
The author synthesizes optical active norepedrine-derivates of MDA via reduction of [alpha]-oxo-oximes with yeast.
Could some Spanish/Portuguese (sorry, don't even know the exact language of this thesis) speaking bee translate the essential parts of the Ph.D thesis and post it?
Thanks alot......
The candle that burns twice as bright burns half as long
(Stranger)
12-29-03 03:20
No 479557
(Rated as: good read)
Need translation of the Cong Nghiep Hoa Chat article mentioned here
Post 398635 (Mountain_Girl: "Methyl Eugenol synth references", Novel Discourse)
http://home.ripway.com/2003-12/43034/Che
http://home.ripway.com/2003-12/43034/Che
http://home.ripway.com/2003-12/43034/Che
In table two (Bang 2) on page 1 the right side is reaction time in hours. It appears that 5 hours is enough to reach equilibrium when mixing CH3OH and H2SO4. Table 1 seems to show that a molar ratio of CH3OH/H2SO4 of 1:1.5 provides the best % yield of CH3SO4H.
(Newbee)
01-04-04 23:29
No 480406
An improved preparation of phenylacetone
Kizlink, Juraj
Chemicke Listy (1990), 84(9), 993-4. (http://hyperlab.0catch.com/ChemickeList
Abstract
PhCH2COMe is prepd. in 52-67% yield from PhCH2COOH, AcONa or AcOK, and Ac2O in the presence of anhyd. CuSO4 at reflux for 24 h.
Here is translation of Slovak article from Chemicke Listy:
Phenylacetone - benzylmethylketone, 1-phenyl-2-propanone, C9H10O, is important intermediate in chemical, pharmaceutical industry and cosmetics. It is prepared by various methods; one branch of them are they using Grignard reagents [1,2], chloroacetone [3] or by saponification of phenylacetonitrile [4,5]. The second branch is based on decarboxylation of phenylacetic acid (or its salts) and reaction with acetic anhydride. For those methods the most determining factor is velocity and completeness of its decarboxylation, which can be improved by various catalysts. Reaction can be conducted by dry distillation of calcium salts of phenylacetic and acetic acid [6,7], boiling of mixture of these acids with alkali acetates [8-10], pyridine or quinoline [11], or methyllithium [12]. Advantageous are also the methods based on passing of phenylacetic-acetic acid mixture over various catalysts as ThO2 [5,13] or MnCO3 [14] at 350-400 C. Crude product is usually purified by fractionation or bisulfite method. Pure phenylacetone has m.p. -15 C, b.p. 215 C, d = 1.0018, nD = 1.5164; its
semicarbazone [8,11] has m.p. 188-198 C, thiosemicarbazone [15] m.p. 155 C, phenylhydrazone [9] m.p. 85 C, 4-nitrophenylhydrazone [16] m.p. 143 C and 2,4-dinitrophenylhydrazone [17] m.p 156 C.
Disadvantageous is long reaction time 24-72 h for liquid-phase methods and workup of the reaction mixture by neutralization with hydroxide, extraction or fractionation of its large volume for all methods. Yields are 30-50 % for liquid-phase methods and 40-65 % for gas-phase methods. The improved method provides yields min. 50 % with shorter reaction time, removing of the neutralization step, and replacement of extraction by easier decantation.
Experimental
To a mixture of 136 g (1.0 mol) phenylacetic acid, 70 g sodium or potassium acetate, and 16 g (0.1 mol) anhydrous cupric sulphate is introduced 2000 ml anhydrous acetic anhydride* in 4000 ml flask. The mixture is refluxed 24 h. After cooling 500 ml of solvent (CCl4, CHCl3, CH2Cl2) is added and the mixture is poured to a flask containing 2000 ml ice-water. After separation of layers upper layer is removed and lower layer is three times decanted with water, separated, dried (Na2SO4, CaCl2), and distilled. The solvent is distilled off and fractionation column is placed on the top of the flask. Remaining acetic acid and acetic anhydride is then removed, pure product is collected at 100 C (15 torr). Yield 70-90 g (52-67 %).
* Technical product, which contains water, can be dried by adding 10 g thionyl chloride.
(Chief Bee)
01-16-04 18:00
No 482852
Could somebody who can read french take a quick look at Bull Soc Chim France 1441 (1963) (../rhodium/pdf /archive/4-ch
I just want a summary of what they are doing, not a full translation (for now).
The Hive - Clandestine Chemists Without Borders
(Hive Addict)
01-16-04 20:32
No 482867
they're comparing the action of Mg on halo-ketals:
in ether the ring is opened to give a glycol-ether
in THF the grignard reagent is formed except for saturated
alpha- or beta-halo-ketals.
i fail to see the connection with chlorobutanal except that
it could give a halo-ketal?
filter(lambda W : W not in 'ILLITERATE','BULLSHIT')
(Hive Bee)
01-31-04 17:39
No 485702
Lego, it says on the first page that it (or at least a part of it) has been released in English:
Baker's yeast Reduction of (E).1.phenyl-1,2-propanedione 2-(O-methyloxime). A Key Step for a (-)-Norephedrine Synthesis. Olyr C Kreutz, Paulo J. S. Moran, José A. R. Rodrigues. Tetrahedron: Assymetry 1997, 8, 2649.
I could translate some part of it. I don't see anything valuable in it though? Which part is it that you are interested in?
-jsx
(Hive Bee)
02-06-04 18:13
No 486912
Could Antoncho or any other HyperLab Bee translate the following post: Post 419906 (Potter: "3-HO-4-Me-P2P èç î-êðåçîëà", Russian HyperLab)
Holotna Pravda... Neskolko dnej iz zhizni siLENZiova
(Stranger)
02-14-04 16:34
No 488612
Russian article needs translation (all or most important points). Aptechnoe Delo (Apothecary's Stuff). Found in Chemical Abstracts 54: 12491e:
http://home.ripway.com/2004-2/71090/Chem
size = 55KB
(5 MB maximum transfer per day for free accounts)
pdf of article and English abstract:
http://home.ripway.com/2004-2/71090/Chem
size = 519KB
Questions:
1) What solvents are used in the liquid chromatography process?
2) Do they determine the concentration of apiole and/or myristicin in solvent or chromatographic fractions by using sulfuric acid as an indicator and then using colorimetry or a spectrometer?
(A Truly Remarkable HyperLab Bee)
02-15-04 16:28
No 488840
From
Spasmolytic substances present in the seeds of Petroselinum sativum.
D. G. Kolesnikov, N. P. Maksyutina, and P. I. Bezruk
Aptechnoe Delo, 7(4), 27-30 (1958).
<Satisfactory analytical data were obtained for the isolated substances.>
For the isolation of apiole, the following adsorption chromatographic method was developed:
Parsley seeds are extracted with ethyl alcohol; after cooling to 10-12 °C, allyltetramethoxybenzene crystallizes out (m. p. 25 °C); the alcohol is evaporated, and the residue is treated with ligroin. The ligroin-insoluble residue (a mixture of flavonoglycosides) is separated, and the ligroin solution is chromatographed on alumina. The eluate (each liter) is monitored using a color reaction with concd. H2SO4, and the content of extractives is determined (probably by evaporating the solution and weighing the residue). The results of the chromatographic separation are presented in Figure 1.
a - fatty and volatile oils; b - apiole and myristicin; c - a substance with m. p. 145 °C.
The oils are eluted first, then follow apiole and myristicin, and the last eluted is the substance melting at 145 °C. Apiole crystallizes easily (m. p. 30-35 °C) after evaporating the solvent and cooling. Its yield is 1.5% of the weight of dry seeds (myristicin 0.6% (liquid), allyltetramethoxybenzene 0.001%).
The authors didn't specify the volumes of ethanol and ligroin used for the extraction, and the amount of alumina. No boiling range is given for ligroin (actually called benzin in the article). The eluent was not explicitly mentioned; one can assume that it was ligroin. - Comments by azole.
(Stranger)
02-16-04 18:22
No 489075
Thanks, azole. BTW, it appears to say in table I that the reaction of H2SO4 with apiole or myristicin gives a red color while with tetramethoxyallylbenzene its colorless.
(Moderator)
02-23-04 03:31
No 490498
From Post 485919 (Zamboni: "Dissertationes Pharmaceuticae", Novel Discourse)
Infrared absorption spectra in the 1-14 micron range of apiole, 1,2,3,6-tetramethoxy-4-allylbenzene, myristicin, etc. obtained from various essential oils are recorded and discussed.
http://home.ripway.com/2004-2/71090/Chem
Chemistry is our Covalent Bond
(Hive Bee)
02-23-04 04:23
No 490511
Thanks, lugh. Here's the abstract from Chemical Abstracts:
CA61:4145b
Infrared spectrophotometric studies of compounds occurring in essential oils. I. Teresa Biernacka, Barbara Kontnik, Andrzej Parczewski, and Zdzislaw Rajkowski (Akad. Med., Warsaw). Dissertationes Pharm. 15(4), 419-26(1963)(in Polish). The infrared absorption spectra in the 1-14 µ range of apiole, 1,2,3,6-tetramethoxy-4-allylbenzene, myristicin, osthole, peucedanin, and alantolactone obtained from various essential oils are recorded and discussed.
(Hive Bee)
06-13-04 20:25
No 513180
Die Synthese optisch aktiver N-Monomethyl-Aminosäuren
P. Quitt, J. Hellerbach und K. Vogler
Helv. Chim. Acta 46, 327-333 (1963) (../rhodium/pdf /n-methyl-amin
Abstract
A synthesis of optically active N-monomethylated amino acids (V) is described. It involves a three-step process, starting from optically active amino acids (I) which are converted into their benzyl derivatives (III), subsequently methylated (IV) and finally hydrogenolyzed. The reaction sequence proceeds without racemization
English translation need ....java
Just hold on to the thread...that keeps us going
http://www.chiapaslink.ukgateway.net/
(Hive Bee)
06-20-04 22:28
No 514450
Can any french speaking bee translate the interesting parts of this article?
No 226. - Recherches en série indolique. XVII. - Préparation de quelques indolines, indoles et tryptamines oxgénés en positions -4 ou -6 par cyclisation "arynique"
Marc Julia, Hubert Gaston-Breton
Bull. Soc. Chim. Fr., 1966, 1335-1342
See also: Post 514448 (Lego: "More on nitrostyrenes and lithium enolates", Tryptamine Chemistry)
Merci beaucoup!
The tendency is to push it as far as you can
(Hive Bee)
07-04-04 19:52
No 517412
Java: which part of the article are you interested in? I would suppose the experimental part? I'm asking because seven pages is a whole lot of text, so I probably will only translate the part desired by you - is it the rxn mechanism/theoretical part or the experimental/preparative part you'd prefer for having translated?
Greetz A
"..ein Trank von unterschiedlicher Farbe, in ihm ist Heilung für die Menschen."
(Hive Bee)
07-05-04 04:09
No 517502
armageddon
The rxn mechanism/theoretical part would be nice to understand the mechanism....thankx..java
Just hold on to the thread...that keeps us going
http://www.chiapaslink.ukgateway.net/
(Hive Bee)
07-12-04 03:47
No 518790
32. The synthesis of optically active N-monomethyl-amino-acids (1)
by P. Quitt, J. Hellerbach and K. Vogler (bumpy english by armageddon)
(7.XII.62)
During the last years, several naturally occuring peptide- and depsipeptide-antibiotics (containing unusual amino acids as building blocks) were discovered. Of these, the N-monomethylamino acids seem to have widespread occurence. For example, N-methyl-L-isoleucin was found in enniatin A (2), N-methyl-L-valin in enniatin B (2) and in actinomycins (3), N-methyl-L-leucin in sporidesmolid I (4), N,beta-dimethyl-L-leucin in Etamycin (3), N-methyl-L-phenylalanin and p-dimethylamino-N-methyl-L-phenylalanin in staphylomycin (6) or ostreogrycin (7) and finally N-methyl-L-phenylglycin in etamycin (5). Both actinomycin and etamycin contain also sarcosin.
Although the preparation of optically inactive or racemic methylamino acids doesn't present any problems, there is currently no satisfying synthesis of optically active methylamino acids. The common method consists in methylation of the tosyl derivatives, followed by cleavage of the tosyl group with sodium in ammonia or boiling hydrochloric acid.
This procedure, developed by FISCHER(8), usually gives partially racemized products (9), so that intermediate products have to be purified via salt formation with optically acitve bases (10). Especially during the methylation with dimethylsulfate or methyliodide (if it is desired to occur in good yield), significant racemization occurs. A tedious separation of the end products is necessary/highly recommended. Also invented by FISCHER(11) but later applied by COOK et al. (9) was the method of replacing bromine with methylamine on optically active alpha-bromo-fatty acids. But even when this method is used, the obtained products were strongly racemized, as we were able to confirm with own experiments.
In contrast to these, the reductive alkylation as performed by BOWMAN(12) on different amino acids using different aldehydes, proceeds without racemization. Although with higher aldehydes, only monoalkyl derivatives are obtained, the use of formaldehyde always results in dimethyl derivative formation(13) or - when only one equivalent of formaldehyde is used - a mixture of mono-, di- and unmethylated products, whereas the desired derivative is obtained only in 5-25% yield and its separation from side products is often very difficult to accomplish (14).
{it follows the reaction scheme:
"Benzaldehyd" is benzaldehyde - obvious...
"oder" means "or"..
"Eisessig" is GAA... (everything else should be self-explaining)}
Moreover, certain N-methylamino acids were made from actinomycines (15). The method described here dips into the principle of reductive alkylation by using benzaldehyde as the aldehyde compound (16). Like shown in the reaction scheme, this leads to a benzyl compound III, which can then be selectively monomethylated. The benzyl-methylamino acid IV, after hydrogenolytic debenzylation, finally gives the desired N-monomethylamino acid V. The benzylidene compounds of the amino acids II are only stable in their salt form and were first isolated by BERGMANN et al.(17) and later by WIELAND & SCHAEFER(18). They don't tend to racemize, a fact which was already observed before by GULLAND & MEAD(19) and by TAGUCHI & ISHIDA(20). Newly, benzaldehyde was also used to protect the epsilon-amino group of lysin (21), as it is easily spit off hydrolytically in acidic solutions.
Compound II isn't isolated, but reduced to the N-benzyl compound III in situ, either catalytically or with sodium borohydride. The isolation of N-benzyl amino acids is accomplished very easily because of their poor solubility (in water) at the isoelectric point {whatever this means!!}. The methylation of the benzyl compound III is done according to the method of LEUCKART & WALLACH (22). This method generally leads straight to the N-benzyl-N-methyl derivative IV which can be isolated - meanwhile, With basic and hydroxyl containing amino acids, side reactions are likely to occur. For example, partial decarbobenzoxylation occurs when N-carbobenzoxy-N-benzyl-L-lysin is treated with hot formic acid, which can lead to partial methylation of the epsilon-amino group. Therefore it is therefore necessary that minimal reaction times are met and that isolation of compound IV isn't attempted. The same applies to the nitroarginin- and the serin derivative, as changes of unknown nature can happen to them as a result of too long reaction times. The kind of methylation procedure implies that after hydrogenolytic debenzylation has occured, the monomethylamino acid V appears in its salt-free form, even if compound IV cannot be isolated. In this last stage, it has to be considered that more hydrogenolysable protection groups can be removed from the molecule if present (Va, Vb). This involves for example the nitroarginin- and the N-carbobenzoxylysin derivative, with which unprotected methylamino acids are obtained without using sodium in liquid ammonia, contrasted to the N-tosyl derivative.
The specific rotations of the starting compounds, intermediates and end products are summarized in the table.
{table}
EXPERIMENTAL PART
1. N-benzyl-L-amino acids - Method A: 0.1 mol of the amino acid are dissolved in 50ml 2n NaOH soln. and 10.1ml (0.1 mol) freshly distilled benzaldehyde are added with good stirring. After 15-20 minutes, the solution has become homogenous. Then, 1.14g (0.03 mol) NaBH4 are added in small portions (alternatively, an aequous solution thereof is added dropwise). The temperature shouldn't exceed 15°C when doing this. After addition is finished, stirring is continued for 1/2 hour, and the procedure is repeated with fresh benzaldehyde and sodium borohydride. Stirring is then continued for 2 more hours before the mixture is washed 2x with ether and brought to pH 6-7 with 1n HCl with good stirring. The benzylamino acid usually precipitates rather quickly and is vacuum filtered, washed thoroughly with water and dried under vacuum. It is usually pure enough for the further reaction steps.
I put my comments into {braces} - I am not sure about the funky amino acid names, so I left them untouched....
Hope my translation is useful to you, java...
Greetz A
"..ein Trank von unterschiedlicher Farbe, in ihm ist Heilung für die Menschen."