  Name       Post

  sunlight   posted 05-28-98 11:00 AM CT (US)
             -------------------------------------------------------------
             In these spring nights, I often dream with the Japanese patent,
             Process for producing phenylacetones (alkyl nitrite in
             corresponding alcohol + safrol + PdCl2 [+ CuCl2 or amine ] =
             MDP2P).  I've dreamed always with methyl nitrite maden from a
             solution of NaNO2 in methanol and water and dropping dilute
             H2SO4. A lot of dreams with CuCl2 cocatalyst and some with
             trimethylamine, and never yield was the claimed in patent. 
             Then I realised desired cocatalyst effect of CuCl2 or 
             trimethylamine never was. Why ? I don't know.  Always Pd Turnover
             ( mols of product/ mols of PdCl2 ) was between 15 to 20, never
             166 as patent claims. So I satarted to dream using

             Some days ago I had a powerful dream :

             1'75 liters of drugstore methanol and 6 grams of PdCl2 was
             bubbled with MeONO produced with a solution of 110 cc of
             methanol, 225 grams of NaNO2 and 300 cc of water (110 cc of
             H2SO4 and 200 of water, chilled was added to the NaNO2 in 2'5
             hours ). With stiring, of course, and with a homemade bubbler
             made with a piece of glass sponge (for feet) welded to a glass
             tube. After the adition of about 200 grams of NaNO2, 100 grams
             of safrol (100 cc of single distilled safrol) was added.
             Catalyst was not dissolved, but the reaction went to 35-40 
             degrees, with a great bubbling of NO and after a while all
             catalyst dissapear. In 30 minutes or so reaction was done, I
             think, and palladium appear again, but all MeONO was bubbled,
             and reaction was kept 2 hours from the safrol addition. Then
             was added 135 cc of water (water is not good before because
             MeONO is less soluble in methanol-water mix, so you need more
             solvent) and was stired two hours more.  Methanol was evaporated 
             at low pressure, the result , with no safrol smell at all (all
             safrol reacted) was basified, what produced a lot of brown tar
             wich was filtered, and extracted with 100, 100 and 70 cc of
             toluene. Toluene was distilled and the ugly deep brown product
             was distilled at 158-165 C with a water pump and all joints
             sealed with silicone products to give ... 81 grams of MDP2P.
             Great !!!  It is a 73 % yield, and I'm sure yield is more,
             because my dream procedures are not exactly academic. Also
             distilling flask was 500 cc to distill 100 cc, so at the end,
             with good temperature, it was impossible to distill some residue.
             No safrol or isosafrol in the product, only MDP2P and more heavy
             products, I think these are something like pyperonyl acetic acid,
             acetaldehyde and others.

             Advantages, no O2 cylinders, easy to done, NaNO2 is OTC or no
             suspicious product, methanol is from drugstore...  Problems,
             don' forget re-direct MeONO and NO fumes out through the window
             with a plastic or rubber tube. Really toxic, but well done, no
             problem at all.  After basic wash a lot of brow tar was formed
             (may be help an acid wash first). Also I did a an error, because
             most palladium was precipited in the flask, so it's time to
             filter and recover this product, may be is reusable (palladium or
             palladium complex ?) but, I prefered evaporate before, and later
             there was not palladium free, all is in the organic layer.
             Finally, this the rest of this strange palladium tar is now in
             the distilling flask.  I think is necessary to boil NaOH strong
             solution to clean it.  But is a good dream. 100 cc of safrol
             single distilled -----> 81 grams of MDP2P.  It's my best one.

             Do you like it for your book Strike ? It's my first one of
             this non-cocatalyst serie.

             Good dreams dear bees.

  Strike     posted 05-28-98 11:45 PM CT (US)    
             -------------------------------------------------------------
             Bra, Strike loves it! Consider your post in the book. And a
             fat copy of the book to you.

             But if anyone else reads this please know that Strike cannot
             come across all these posts. If you have something you want
             printed, please email or mail Strike the document.

             All you bees with something to add REALLY have to submit very
             soon or you will miss the publishing deadline!

  sunlight   posted 05-29-98 02:41 AM CT (US)
             -------------------------------------------------------------
             Ok, may be in a week I can give simplified and better
             directions to do this expierence.

  quirks     posted 05-29-98 06:41 AM CT (US)    
             -------------------------------------------------------------
             Great post....

             NaNO2 is available OTC as meat perservative no? and did I
             hear "stump remover" from someone before??

             <<
             1'75 liters of drugstore methanol and 6 grams of PdCl2 was
             bubbled with MeONO produced with a solution of 110 cc of 
             methanol, 225 grams of NaNO2 and 300 cc of water (110 cc of
             H2SO4 and 200 of water, chilled was added to the NaNO2 in 2'5
             hours ). With stiring, of course, and with a homemade bubbler
             made with a piece of glass sponge (for feet) welded to a glass
             tube. After the adition of about 200 grams of NaNO2, 100 grams
             of safrol (100 cc of single distilled safrol) was added.
             Catalyst was not dissolved, but the reaction went to 35-40
             degrees, with a great bubbling of NO and after a while all 
             catalyst dissapear. In 30 minutes or so reaction was done, I 
             think, and palladium appear again, but all MeONO was bubbled,
             and reaction was kept 2 hours from the safrol addition. Then
             was added
             >>

             So after the pallidium appeared, you stirred for two more
             hours. Then you added water and stirred for two more hours
             again. At the end of the rxn, is the PdCl in or out of
             solution?? When is the best time to recover the PdCl??

  sunlight   posted 05-29-98 07:56 AM CT (US)
             -------------------------------------------------------------
             Not exactly. In my dream first I added to NaNO2 solution
             almost all the H2SO4 solution. It's important the bubbles to
             maximize absortion of MeONO in methanol. I think the limit is
             8-10 grams per 100 cc of methanol. Then the solution has all
             the MeONO needed, I suppossed, what took about 1 and half
             hour, and safrol was added. Started a slightly exotermic
             reaction and the rest of MeONO was bubbled. After the
             addition of safrol the reaction was kept two hours, I think
             one hour and half is enaugh. Then water was added and stired
             two hours more. It's good to warm reaction a bit, if
             possible, but not necessary, it helps hydrolisis.
             Sometimes precipites palladium, normally when water is added
             if there is not a lot of methanol. This time, may be the most
             part of MeONO reacted in the first half hour, and palladium
             precipited. I don't know why, but I think is because there is
             no MeONO to react and recover palladium, some strange complex
             are there. Even in the patent is said that the function of
             nitrites is not clear.
             I precipitate occurs, it's time to filter. I think is not Pd
             metal, but Pd organic complexes.
             I don't know if it can be reused. May be.
             If you filter now, sure you avoid a great part of the tar.
             All safrol was reacted, and no smell of isosafrol, only
             ketone and other little byproduts.
             Sure some night I'll have a simplified dream, you will know
             it.
             BTW, in #3, i think things are similar, the extracted phase
             will be deep red-brown, after basic wash a lot of precipitate
             will be formed, and when distilling a lot of ugly brow tar
             will make the falsk really difficult to clean, or not ?

  sunlight   posted 05-29-98 08:04 AM CT (US)
             -------------------------------------------------------------
             The bubbler is important. It's important to get a lot of
             little bubbles to maximize absortion of gas.
             Other one. Filter after hydrolisis and before evaporation.
             After evaporation, with the temperature, all palladium goes
             back to organic phase.
             Sorry

  quirks     posted 05-29-98 09:33 AM CT (US)    
             -------------------------------------------------------------
             Ok, please forgive my stoopid questions, but
             do you think it would be possible to use slightly less Pd
             with a longer reaction time?? Say 4g/100g safrole??

             And, me being likely to f*ck up several times before getting
             things right, can I add the PdCl2 to the MeOH/MeONO after the
             MeOH is saturated?? ie instead of bubbling the
             PdCl2/MeOH soln and possibly screwing up
             and losing precious PdCl2.

  TaRa       posted 05-29-98 02:11 PM CT (US)    
             -------------------------------------------------------------
             Sunlight: Great variation to process #3. Could you write a
             more simplified step by step procedure of this. I think it
             has great potential, just needs a little more explanation for
             those of us that are a little slow at grasping chemical
             concepts (We're chemically challenged so to speak) ;o)..

             Thanks in advance

  Osmium     posted 05-29-98 02:26 PM CT (US)    
             -------------------------------------------------------------
             US Pat. 4638094 : Process for producing phenylacetones
             For all of you who don't know what he's talking about.

  quirks     posted 05-29-98 06:48 PM CT (US)    
             -------------------------------------------------------------
             http://www.lycaeum.org/~rhodium/chemistry/mdp2p.abstracts.txt

  Mr X       posted 05-30-98 11:50 AM CT (US)    
             -------------------------------------------------------------
             Great one Sunlight!

             You haven't mentioned temperatures. Did you keep the reaction
             at room temp? Did you cool the flask down when bubbling MeONO
             in, to maximize absorption?

             You how fast does the MeONO evaporate away, do you need to
             keep bubbling all the way through the reaction or at
             intervals?

             I would think this could be done in a pipe bomb , this way
             you wouldn't have to keep bubbling in MeONO.

             MeONO is bubbled into chilled methanol to maximize
             absorbtion, add your catalyst and safrole, then let react
             (under pressure from the bomb) at room temp. or maybe with a
             bit of heat (or would you get more polymerisation with heat?)
             Some shaking is also needed. After a few hours add water to
             hydrolyize and work up. Could give you a better yield.

             BTW, I like the sponge idea ;)

  quirks     posted 05-31-98 12:49 PM CT (US)    
             -------------------------------------------------------------
             The alkyl nitrites can be prepared by bubbling N2O3 gas
             through them, ala pugsley can't they?? ie use stump remover
             instead of NaNO2. Stop when the weight reaches the desired
             concentration.

  sunlight   posted 06-01-98 04:28 AM CT (US)
             -------------------------------------------------------------
             Well, a lot of questions.
             This procedure is in the japanese patent in the Osmium post.
             All examples will cocatalysts doesn't run (?), give yields as
             only PdCl2 were present in reaction. So I've tried with 6 %
             molar PdCl2 and no catalyst, is also in the patent. What I've
             done is to reduce the amount of solvent, in the patent uses
             0'5 l. of methanol to 16 grams of safrol.
             I think this reaction done as Uncle Fester SOMM with plenty
             catalyst will give similar yields, but make the basic wash
             after evaporation, becuse palladium is not in water, but in
             organic phase. Other difference is that I prefered to add
             water later, also is a variation present in patent, because
             I've found MeONO is more soluble if there is'n water, and
             yields are better.
             I think there's no problem with bubbling MeONO in methanol
             with the PdCl2, but it can be added later if you want. Also
             safrol and PdCl2 can be added before adding MeONO, I've added
             safrol later because then is a excess of MeONO and probably
             the reaction works better, quick and safe. but may be works
             the same. With a small quantitie I've tried this variation
             also, then I didn't distill, but the product smell nothing
             similat to safrol (MDP2P), what means reaction is also ok.
             Methanol can be chilled and so absortion is great. The
             problem in the absrtion question is to know when are is the
             flask the 2 or more mols of MeONO needed for each mol of
             safrol. With small quantities I weighed the flask each 15
             minutes or so till the weight was the desired. So I observed
             absortion at room temperature, about 20 C is about 8-10 grams
             of MeONO per 100 cc of methanol. Also is needed some bubbler,
             if not, you must increase the amount of MeONO bubbled in
             reaction, cause absortion is slower.
             There are a lot of combinations. I'll try the singlest one
             and you will know it in a few days. I think may be is not
             important safrol is before or later MeONO, what is important
             is enough PdCl2 and enough MeONO.
             Also I think PdCl2 can be reduced a bit. In other reactions
             I've foun Pd Turnover of abut 20-25, wich means may be 4 or 5
             % could be enough. I'll try. Just a few days.
             I'll post a complete recipe, quantitites, temps, time, etc...
             After 8 months, I'm starting to enjoy.

  Osmium     posted 06-02-98 05:35 AM CT (US)    
             -------------------------------------------------------------
             I'd use EtONO. Boiling point around room temperature, and
             better absorption.
             Keep the water content low, reaction will be faster. And
             dissolve the Pd cat. properly, it takes quite some time to
             dissolve completely.
             Use the bisulfite for purification. O. had a powerful
             explosion when O. tried to distill it.

  sunlight   posted 06-02-98 07:09 AM CT (US)
             -------------------------------------------------------------
             Well Osmium, I know you are a great Bee, and I've learned
             with you . Like me, you can learn with my experience.
             I have dreamt with this rxn 20 times more or less, with all
             the possible variations I've found.
             EtONO, yes I tried with Eleusis and UF recipe. Boiling point
             is 17 C, so when you have finished rxn, separating layers,
             you have a mixture of sodium sulphate crystals in chilled
             water and in the top the nitrite, but the crystals don't pass
             through the hole in the sep funnel. So EtONO starts to boil
             in a few minutes. I got stoned and intoxicated. MeONO runs
             OK, and is done in situ, less time, less work.
             No water, it increases solubility of MeONO in methanol. After
             water to hydrolize.
             6 grms of PdCl2 couldn't be dissolved in 1'75 liters of
             methanol in about 2 hours, but this is not a problem,
             catalyst don't need to be dissolved to react, I've seen how
             it react and dissolves during rxn.
             You are the second person that reports an explosion
             distilling product with this rxn. I've distill it six or
             seven times with no problem. Only that when PdCl2 was 0'5 %
             or 1 % or 2 %, most part of distillate was safrol and others,
             with 6 % all is ketone, but always the flask needed a hard
             work to clean.
             Otherwise, bisulphite is a good alternative. You can help me
             now, once I dreamt with bisulphite addition and it yielded 7
             grams. I put it in 10 % NaOH and shaked it, but there wasn't
             two layers, but a strange emulsion, like ketone didn't want
             to go out.
             How do you do it ? May be is better adding HCl and don't
             breath fumes?

  Osmium     posted 06-02-98 07:44 AM CT (US)    
             -------------------------------------------------------------
             NaOH is much better than HCl. Extract it.

  Labrat     posted 06-02-98 10:07 AM CT (US)    
             -------------------------------------------------------------
             Sunlight: have you ever heard of Uncle Fester's SECRETS OF
             METHAMPHETAMINE MANUFACTURE. Your so-called new method was
             long ago described by Uncle Fester, so actually you're sort
             of stealing it from this guy, aren't you? Sure, it is the
             best way to convert safrole into MDP2P, but Uncle Fester has
             given instructions following the patent. The only new thing
             he came up with was bubbling methylnitrite into the reaction
             mix instead of making the nitrite first and adding it in
             liquid form. That's why your yields are low! That
             methylnitrite is so freaking volatile, you'll lose most of it
             before it reacts so you have to use a 2-3 molar excess.
             Substiting isopropanol for methanol gives a nitrite that is
             easier to handle and gives higher yields at 30 dg C. Well, if
             that's what it takes to get in Strike's book, I have a good
             "NEW" method which embraces electrochemical epoxidation of
             isosafrole and then isomerisation to the ketone with LiI...
             interested? Lr/

  quirks     posted 06-02-98 11:21 AM CT (US)    
             -------------------------------------------------------------
             Labrat: I'm sure he's heard of it, but not nessacarly all
             people have access to places selling SOMM or the language
             skills to read it. As much of a utopia as I'm sure it would
             be, the whole world is not the US.

  fudd       posted 06-02-98 12:30 PM CT (US)    
             -------------------------------------------------------------
             Has anybody tried this with isopropyl nitrite? It would seem
             that this would be even easier to work with than EtONO, since
             you'd think it would have an even higher boiling point.
             However, what would happen with steric hindrance, etc.? Any
             ideas?

             -fudd

  fudd       posted 06-02-98 01:34 PM CT (US)    
             -------------------------------------------------------------
             IPA seems, theoretically at least, to be the alcohol of
             choice. The nitrite produced had a boiling point around 40
             deg C, so it could easily be distilled. The distillate could
             then be simply poured into the reaction flask. Less solvent
             would be needed, so larger batches wouldn't be as limited by
             the avaiability of oversized reaction vessels. On top of all
             of this, due to its ease in transportation, it would make a
             great substitute for poppers!

             Does anybody have any feelings about this?

  fudd       posted 06-02-98 05:25 PM CT (US)    
             -------------------------------------------------------------

             Say, what if you used IPA to make the nitrate, then poured it
             in like Labrat said, then bubbled the exhaust from the
             reaction flask into a bucket of NaOH or something. Would this
             be a clean enough process to be done in a bathroom or
             kitchen?

  r2d3       posted 06-02-98 08:46 PM CT (US)    
             -------------------------------------------------------------
             WHAT IS THE MATTER WITH YOU PEOPLE?

             Sunlight clearly stated in his first post that his was
             posting results from a Japanese patent, not trying to post as
             his own work. He has done his best ( in obviously a second
             language ), to inform you of what happened. With all the
             garbage posted here, so easy to flame, it surprises the hell
             out of me why there are people who want to start a pissing
             contest over this valuable information.

  Q10        posted 06-02-98 10:19 PM CT (US)    
             -------------------------------------------------------------
             r2d3: I couldn't agree with you more. I hope more people feel
             the same as we don't want to discourage positive and
             intelligent input.

             Sunlight: Thanks for the input.

  Osmium     posted 06-03-98 03:00 AM CT (US)    
             -------------------------------------------------------------
             When using ethyl nitrite, it can be generated in a external
             gas generator and distilled into the reaction by placing the
             generator in a warm water bath. It will dissolve in the
             alcoholic solution very well.
             Using IPA-ONO doesn't avoid problems, at least when the
             reaction solvent is MeOH. In alcoholic/MeOH solutions both
             nitites, that of MeOH and that of IPA, will be present.

  sunlight   posted 06-03-98 03:24 AM CT (US)
             -------------------------------------------------------------
             Labrat, I think I haven't said this is a new method. And you
             can read in one of my posts :

             I think this reaction done as Uncle Fester SOMM with plenty
             catalyst will give similar yields, but make the basic wash
             after evaporation, becuse palladium is not in water, but in
             organic phase. Other difference is that I prefered to add
             water later, also is a variation present in patent, because
             I've found MeONO is more soluble if there is'n water, and
             yields are better.

             I started with SOMM, of course, but with the prefered method
             as UF say, what means a 0,5 % PdCl2 and a 2,5 % CuCl2.
             Well, this method yields about 3 % MDP2P.
             Also trimethylamine was tried, and a lot of variations since
             I understood may be the problem is in PdCl2 amount.
             I have read never a post with good yields in this method, so
             I posted my dream. Just because I want all the bees to know
             what really runs, and what doesn't run. As a contribution,
             not as if I were a great chemist, what obviosly I'm not.
             What about methyl nitrite ? I buy methanol OTC, and is one
             step reaction. Yields in patent are 91 % but analyzed before
             any extraction. I said I have losed some materials with my
             poor methods. For me 81 grams from 100 cc of safrol is the
             best I have done never. May be it's usual for you, but not
             for me.
             What we need is real reports, what I want is to share what I
             have found with Japanese _ SOMM method.
             May be you like to compete, but I prefer to learn what is
             single and easy. And safer.
             Don't compete, but collaborate. We all are one.

  sunlight   posted 06-03-98 08:29 AM CT (US)
             -------------------------------------------------------------
             Labrat, I want to explain you somethings about SOMM. As I've
             said, I started with the cheaper method in the book, wich
             definitively don't run. Fester say is the best. I asked
             Fester about this, but he couldn't say anything, because he
             hadn't done. I know also some people who have tried it, and
             after some attempts, they abandon.
             Fester is wrong in this point.
             Well, I had then a lot of questions about why is the reason
             rxn didn't run ok. I thought about absrtion of methyl
             nitrite, so I started to dream with small quantities. To be
             sure, I decided to put first nitrite , weighing the exact
             amount of nitrite before adding safrol. But rxn didn't run.
             Now, with a quantittie I can't weight, it's the same to make
             this in one way or in the other, both are good, and I must
             say you in the rxn I've dreamt, all safrol reacted, 100 %,
             yield is not low for this reason. Also I'm sure yield was
             higher, but evaporation, washings, filtration and
             distillation in a too much large flask, obviously means less
             product.
             I thought sometimes this rxn is wrong and never yield
             nothing. I know other people who have tried with no results
             and they abandon as I've said.
             I finally realised that rxn runs, but depends only of PdCl2
             amount. Cocatalysts effects don't run, unfortunately. If you,
             or other bee can discover how to do it, it would be
             fantastic. 1 gram of PdCl2 and 4'25 of CuCl2 for 1 mol of
             safrol.
             So I tried with 6 %l catalyst, first with a test. I bubbled
             then nitirte into safrol - methanol .Yields were good. Fester
             is right now.
             After this, I dreamt with 100 cc of safrol. Then I decided to
             put first nitrite. Why ? Because was the only way to know all
             nitirite is in the flask, and I have reasons to doubt about
             Fester's procedure.
             To simplify, next try will be bubbling into safrol -
             methanol.
             So, what I'm saying is that rxn with plenty catalyst runs,
             what was very doubtable for me and for others.
             I have never heard this rxn runs, only people said rxn
             doesn't run. It's easy, and I think what I say it's
             interesting.
             Fester's procedure is intelligent, so I use it. But Fester
             don't know exactly the reaction. For example, palladium is in
             the organic phase. If you don't wash it with dilute NaOH you
             will have a lot of palladium in the distilling flask, two
             person have reported an explosion in distillation, may be for
             this reason. Fester procedure is partially ok, not
             completely. There are many errors in SOMM, so it's
             interesting to clear up things.
             May be all people know this rxn, may be this report is
             unnecessary, then excuse me.

             BTW. Mr X, yes chilled methanol increase (of course)
             absortion of MeONO, Ive done it. Working with small
             quantities it's possible to weight absortion. But I want to
             try a general method. As Fester, but tested. If you don't
             have enough NaNO2, chilled methanol reduce the amount needed
             to 2/3 parts more or less.

  Labrat     posted 06-03-98 09:00 AM CT (US)   
             -------------------------------------------------------------
             OK Sunlight, it's a good thing you tried the patent procedure
             and found out things didn't run as was stated. That's always
             a good thing. Practical experience is about as valuable as a
             new theoretical procedure. But what really pissed me off
             yesterday was that you practically copied Fester's method out
             of PRACTICAL LSD MANUFACTURE! It was even more distressing to
             me, cuz I wanted to post some more on this reaction too.
             Fester presented this reaction as was it something new. It's
             not new and known for a long time: it's called the
             Wacker-process. This process is used to make acetaldehyde
             from ethylene. The patent is new in the aspect that it covers
             an alcoholic Wacker process, with an alkylnitrite as a
             reoxidant for the palladium salt. I have some pretty good
             refs on Wacker oxidation wherein a lot of good theory is
             worked out in detail. But since you posted on this subject
             first, you get the credit for it and I will not elaborate
             further. Damn shame for all the work I put into it. Now you
             gettit why I was a bit cranky? Good. Lr/

  quirks     posted 06-04-98 10:58 AM CT (US)    
             -------------------------------------------------------------
             sunlight: in your many dreams have you tried using straight
             sassafrass oil?

  sunlight   posted 06-04-98 12:16 PM CT (US)
             -------------------------------------------------------------
             No, never. safrol is single distilled, wich is a single
             procedure if you can distill. May be it will run.
             Otherwise, if you can't distill (with a water pump in this
             case), you will have a problem with the ketone because is
             plenty of Pd byproducts. When this brown product is in
             aluminium, impurities can stop rxn and you must add then a
             bit of NaOH. It runs, but you must purify your brown honey
             recrystallizing a few times. (Hot acetone or hot IPA and then
             acetone)
             Of course distillation is better, or as Osmium say,
             bisulphite recovery. This might do skip both distillations...

  TaRa       posted 06-04-98 01:21 PM CT (US)    
             -------------------------------------------------------------
             Sunlight : Could you please clarify a few basic points;

             In setting up this rxn, you added the Methyl alcohol + PdCl2
             to a 3-4 liter flat bottom flask and started stirring? Best
             to use 2 neck flask; one for addition of safrol the other for
             gas dispersion tube (bubbler)? Does temp need to be
             monitored?

             Then set up a gas generator to make the MeONO gas in? The
             PdCl2+MeOH is stirred and to this solution you bubbled in the
             MeONO gas?

             The Methyl alcohol (chilled)+NaNO2 was dissolved and was
             added dropwise to the dilute H2SO4 at the medium rate (to
             create the MeONO gas)??. How did you tell when 200 grams of
             NaNO2 was added? Since it's in solution with the MeOH? In any
             respect the gas generated was bubbled into the alcoholic
             PdCl2 solution. When approximately 4/5 of the alcoholic NaNO2
             was used up (added to the H2SO4), you add the safrole?

             How long did it take to bubble that much MeONO gas into the
             solution?

             After the safrol you stir for an additional 2 hours (then
             hydrolyze with H2O)?

             Great post - thanks in advance..

  sunlight   posted 06-05-98 03:58 AM CT (US)
             -------------------------------------------------------------
             Please wait till next week. I've had another dream, but this
             time bubbling MeONO directly in safrol+PdCl2+methanol, as the
             patent say, and Fester. It also works and is easier, I put
             safrol after nitrite because I wanted to be sure all nitrite
             is in rxn when safrol is added.
             In this new rxn, 150 cc of safrol are in 1'75 liters of
             methanol and 8'5 grams of PdCl2. Then was bubbled MeONO
             produced with 280 grams of NaNO2. 2 1/2 hours, (no safrol in
             rxn, smell different , funny !!! ) then 200 cc of water was
             added. I must distill now, but I'm sure I have more than 120
             grams of ketone. Also I've realised when 5 or 6 % catalyst is
             present in rxn ( is my third attempt, first one with 16 cc of
             safrol )
             MeONO reacts very quick, solvent and NaNO2 can be reduced
             more. But it will be
             my fourth dream.
             Till next week. May be I can find a translator to express me
             better. It's a hard work.

  Piglet     posted 06-05-98 04:34 AM CT (US)    
             -------------------------------------------------------------
             Sunlight: Nice one man. That is a very attractive route. I
             notice that you use more water & less methanol than Fester.
             Is there a reason for that ?
             As Osmium alluded to, can the ketone be seperated with
             bisulphite ? If you arn't bothered about recycling the
             catalyst and just want the product...
             I wondered about cooling & filtering the product mixture,
             adding water & bisulphite then filtering again, throwing out
             the junk...

             All the best,
             Piglet :)

  sunlight   posted 06-05-98 06:20 AM CT (US)
             -------------------------------------------------------------
             > I notice that you use more water & less methanol than
             Fester. Is there a reason for that ?
             1) I've observed that water decrease MeONO solubility, so if
             you put only methanol, you can work with less solvent, wich
             means less time evaporating it.
             After rxn with nitrite is done, we must add water to
             hydrolize dimethoxy derivative of safrol to the ketone. Then
             is nice to add water. But still is less than in SOMM, because
             a lot of water can make a separation of phases, dificulting
             hydrolisis.
             2) If you done the reaction as Fester, with methanol and
             water in the flask all time, yields in the patent are 83 %,
             but if only methanol is present and after water is added,
             patent claims 91 %

             >As Osmium alluded to, can the ketone be seperated with
             bisulphite ? If you arn't bothered about recycling the
             catalyst and just want the product...
             I wondered about cooling & filtering the product mixture,
             adding water & bisulphite then filtering again, throwing out
             the junk...

             I've made bisulphite addition when product is isolated, with
             no distillation. Of course it runs. I've also thought as you
             about to add
             directly saturated bisulphite solution to the reaction, but I
             haven't done, Two reasons, first is I don't know what is
             solubility of bisulphite in methanol, the other is I think
             that when Na in solution, as bisulphite is a weak acid, this
             will make hydroxydes precipitate as tar (just as basic wash)
             but I don't know. As you see, there are a lot of ways to
             investigate.
             I don't like distill at low pressure, but seeing these brown
             products I am surrended.
             Let's go on

  Piglet     posted 06-05-98 08:43 AM CT (US)    
             -------------------------------------------------------------
             I have just done some reading and have a few suggestions for
             you all to throw around...

             1. Sunlight adds his water after all the safrole has formed
             an intermediate. I suggest that this may lead to more
             polymerization since there will still be some nitrites &
             nitrogen oxides in the brew and these are quite reactive
             compounds. This leads me to...

             2. I have read that you must distill off the methanol under
             reduced pressure because of the nitrites & nitrogen oxides
             which screw around with the product. Can these compounds be
             destroyed in some simple fashion ? These are most likely the
             compounds that explode.

             3. I am guessing that sunlight is from europe. If so, AMYL
             nitrite (pentyl nitrite) can be purchaced from head/rave/sex
             shops. If you buy in bulk, it is quite cheap.
             This has a B.P. high enough to prevent fumes being a problem.
             No need for the gas generator. Less can be added as none will
             be lost.

             4. This is a crazy idea but... what if you added hydrogen
             peroxide instead of water ? I don't know but maybe it will
             form less dimers etc.

             5. If you CAN remove the dodgy nitrogen compounds, can you
             just add bisulphite to the methanol (maybe add more water as
             well).

             These ideas are just that. My angle is 'just how simple can
             this reaction be made'.

             Thanks for your replys and keep up the good work, Sunlight!

             All the best,
             Piglet :)

  Piglet     posted 06-05-98 09:27 AM CT (US)    
             -------------------------------------------------------------
             Oh yes, I also thought about those nasty nitrogen oxides in
             terms of N2O3... Maybee the pseudonitrosite is being formed.
             This would certainly form a nasty tar. Again, maybee a little
             water in the methanol/nitrite solutiion might be good ?
             Check out Rhodiums site for a good overview of these
             nitrosites.

             Lets keep hacking...

  sunlight   posted 06-08-98 06:24 AM CT (US)
             -------------------------------------------------------------
             I have just done some reading and have a few suggestions for
             you all to throw around...

             1. Sunlight adds his water after all the safrole has formed
             an intermediate. I suggest that this may lead to more
             polymerization since there will still be some nitrites &
             nitrogen oxides in the brew and these are quite reactive
             compounds. This leads me to...

             > Well, patent says it will give higher yields.

             2. I have read that you must distill off the methanol under
             reduced pressure because of the nitrites & nitrogen oxides
             which screw around with the product. Can these compounds be
             destroyed in some simple fashion ? These are most likely the
             compounds that explode.

             I haven't had never explosions. Nitrites and NO fumes goes
             out easily when adding water and when adding vacuum.
             Explosions have been reported distilling product. If you
             don't wash you will have a lor of tar, may be it's the
             reason.

             3. I am guessing that sunlight is from europe. If so, AMYL
             nitrite (pentyl nitrite) can be purchaced from head/rave/sex
             shops. If you buy in bulk, it is quite cheap.
             This has a B.P. high enough to prevent fumes being a problem.
             No need for the gas generator. Less can be added as none will
             be lost.

             > Good observer. I'm from Europe. But I don't want to buy any
             chemicals, only OTC and the minimum amount of otheres. Amyl
             nitrite is a "strange chemical" for a normal citizen, and
             requires amyl alcohol, wich is other chemical. And it's no
             really cheap. Fumes are not a problem if you do things right.

             4. This is a crazy idea but... what if you added hydrogen
             peroxide instead of water ? I don't know but maybe it will
             form less dimers etc.

             > No idea.

             5. If you CAN remove the dodgy nitrogen compounds, can you
             just add bisulphite to the methanol (maybe add more water as
             well).

             > May be, but I have only nightmares with bisulphite
             (metabisulphite)

             These ideas are just that. My angle is 'just how simple can
             this reaction be made'.

             > See last version, I think it's the best and simple to get
             more than 70 % yield, (>80 % in weight from safrol)

             Thanks for your replys and keep up the good work, Sunlight!

             > Thanks for your interest and suggestions.

             Oh yes, I also thought about those nasty nitrogen oxides in
             terms of N2O3... Maybee the pseudonitrosite is being formed.
             This would certainly form a nasty tar. Again, maybee a little
             water in the methanol/nitrite solutiion might be good ?
             Check out Rhodiums site for a good overview of these
             nitrosites.

             > Yes, some tar may be this kind of products. Patent runs as
             I do, and yields are enough good. I think also Pd reaction is
             quicker than nitrosite one, so, equilibrium of reactions is
             clearly in the side of Pd oxydation.

             Good dreams for you.

  Piglet     posted 06-08-98 10:34 AM CT (US)    
             -------------------------------------------------------------
             S:

             1. I have only seen the fragments on Rhodiums board. Could
             you post the patent (or send it to rhodium to post)

             2. I just made the point for people without vaccum
             aspirators. (like me)

             3. Amyl nitrite IS OTC. Easier to get than NaNO2 I
             think...(in the U.K. anyway)

             4. Pure rubbish on my part!

             5. I will test out bisulphites in methanol soon...

             6. N2O3 is very reactive. Relativly, who can say (not meee!)

