Author Topic: Medium scale performic  (Read 11546 times)

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baalchemist

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Medium scale performic
« on: April 14, 2001, 01:48:00 PM »
Baal recently ran a performic reaction at the 750g scale and this is how it went;
750g-Iso,231g-baking soda,2310ml-DCM were placed in a 5L
flask w/condenser and stirred for 3 hours. A mixture containing 718g-35%H2O2,1154g-86%formic acid was dripped in through top of condenser over ~2 hours. Mixture was allowed to stir a total of 24 hours. Bottom DCM layer was removed and top acidic layer was extracted with DCM and added to the other. DCM was rotovap'd off and remaining syrup was placed in a flask and 5000ml-15%H2SO4 was added,then quickly heated to 75c and allowed to stir 2 hours. Mixture was cooled and allowed to seperate, bottom layer was removed and aqueous layer extracted with DCM. The bottom layer and DCM extracts were combined and washed 7 times W/H2O to remove excess acidity. This was then vaccum distilled to yield 596g's of ketone. Normally Baal would have used 7500ml for hydrolysis,but 5000ml was used in experimentation, it worked excellent.

Dope_Amine

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Re: Medium scale performic
« Reply #1 on: April 14, 2001, 05:03:00 PM »
Very interesting baalchemist!  I was actually planning on making a thread to clear up the conflicting reports with whether one was supposed to add the sodium carbonate to the hydrogen peroxide first or whether the formic and hydrogen peroxide were supposed to be mixed first.  Yea, and also in the article on Rhod's page, they mention the use sodium carbonate, not sodium bicarbonate but that's another issue.  I also cut the amount of sulfuric way down.  It's overkill and when you are doing somethin' over 500 g isosaf, it's a rediculous volume.  But anywayz, good job!  ;)


something for your mind.......

baalchemist

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Re: Medium scale performic
« Reply #2 on: April 14, 2001, 05:45:00 PM »
Yeah when you start multiplying the numbers for scale-up, that H2SO4 amount gets very excessive. Thats always kept it at 500g max with Baals 5L glassware,decided to go out on a limb this time for research's sake. The yields are so damn consistent with this route it amazes me sometimes. Its gotten to be a real no-brainer these days.

Rhodium

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Re: Medium scale performic
« Reply #3 on: April 14, 2001, 05:58:00 PM »
DopeAmine: Could you elaborate more on your experiments with the modified performic? I am very interested in this method and would like to have a more detailed/extended writeup of it on my page (the same goes for Mr Baal).


http://rhodium.lycaeum.org


baalchemist

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Re: Medium scale performic
« Reply #4 on: April 14, 2001, 08:08:00 PM »
It seems Baal had some more distilling left to do, total yield ended up being a whopping 672g's!!> from 750g-ketone. The leftovers in the flask are still quite fluid, I bet there's still another 15ml's still in there. It seems that reducing the volume of that H2SO4 did the trick. That is a personal best for this method. I will post a more formal write-up if thats what your looking for Rhodium.

baalchemist

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Re: Medium scale performic
« Reply #5 on: April 15, 2001, 12:06:00 AM »
Baalchemists Performic procedure went as follows;
First 750grams-Isosafrole was placed in a 5L flask along with a 3 inch stirbar,commenced to stir on high. Then added
231 grams of (arm&hammer)Baking soda(Sodium Bi-Carbonate,Bicarbonate of soda,etc..) followed by 2310ml's of DCM(distill from stripper). A cold water condenser was placed on the flask and mixture was allowed 3 hours to stir. Meanwhile the Performic acid  mixture was prepared by adding 718grams of 35%-H2O2 to 1156 grams of ~86%-Formic acid,with good stirring. The 5L flask that has been mixing away is fitted with an addition(or Seperatory) funnel and filled with the Performic acid mixture. The addition is started with a good steady drip rate of about 4-5 drops per second. It will soon become somewhat exothermic and a slight reflux will be noted, along with a color change to yellow then on to orange.Starting with the beginning of the addition, a total of 24 hours this mixture is allowed to stir on high speed. After the 24 hours, stop stirring and let it settle into its 2 layers, and remove the top Performic acid layer and extract it in a sep funnel with 200ml DCM. Add the DCM extract to the 5L flask with the bottom layer in it. Then either distill or rotovap off the DCM, leaving a dark orange syrup. 5000ml's of 15%-H2SO4(made by diluting 93%-H2SO4 drain opener) was heated to 75c and then added with stirring to the orange syrup in the 5L flask, add the condenser once again(but not necessary).
This was then held at 75c and stirred on high for 2 hours exactly. This was removed from heat and stirred until it cooled down to room temp. Stirring was halted and it was allowed to seperate into its 2 layers once again. The dark bottom layer is then removed, and the top layer extracted with 250ml-DCM>2X. DCM extracts were added to the dark bottom layer along with an additional 250ML-DCM. This was then washed with an equal portion of H2O a total of 7x to remove excess acidity & whatnot. The DCM is then removed via roto-vap or distillation. The resulting viscous oil was
then vaccum distilled at ~140c, yielding 672 grams of a light golden ketone. This has been Baalchemists highest yield percentage to date using this method. The only difference this time, was the amount of 15%-H2SO4 used in the hydrolysis part of the reaction. Based on the original reaction details, 7500mls would be necessary for a reaction this size. These results prove different to the advantage; less volume with higher yield potential. Baal makes his own Formic acid on occasion, it works with comparable results. A suggestion if using 77%-homemade Formic acid,add an additional 10% volume to help compensate for not having 86%. The same goes if using 30%-H2O2,add an add'l 5%.
This reaction was done in a room that was ~20c in temp.
Baal is unsure of exact vaccum measurement,but its 28-29".
This is basically bullet proof if done exactly as written here.

LaBTop

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Re: Medium scale performic
« Reply #6 on: April 15, 2001, 12:52:00 PM »
Rhodium, I'm flabbergasted!
Did you really miss all these months and years my write up for the Classic Performic acid method ?
The first one I posted in the first One Pot MDMA/NaBH4 thread in begin 1999! You can find that one back at the end of my following write-up. That was the one where for the first time the use of SodiumBIcarbonate was mentioned by me, in contrast with Ritter, who used Sodiumcarbonate, and a different method of preparing the mixtures.
Then a VERY extensive write-up I posted in my Detailed Methods for NON-Chemists, IT's DONE sticky threads in the Newbee and Methods forums.
They hang there allready nearly a YEAR !
Notice a few things there:
1. I start with 16.25 gram Isosafrole, end with 16.00 gram pure MDP2P, I also gave a w/w and mole % !
2. I allready explained that you only needed half of the 15% H2SO4 solution from the original reference, to safe a lot of waste!
3. My write-up is exactly the same as Baalchemists, only much more explained, there are no differences at all, chemically spoken.
So did he follow this write-up, yes or no?
4. I have multiple times explained in many threads here that in my opinion this method is the most easiest, most consistent and secure method to get real pure ketone. Why did you never take notice of them, while you declare now to be very interested in it?
5. Already in 1999 it was posted by Gyrogearloose that my form of the Performic worked better than Ritters, he even got into discussion with Ritter about it, but his use of the english language gave way for some misunderstanding at first, because both participants did not understand that they both talked about a different interpretation of the performic.
They both thought to be talking about one method, but they weren't.
At the end of my write-up you see Ritter declaring again that his write-up works better, but I disagree, the way I explained it gives consistently higher yields. If I remember right, also Methylman and some others have followed my write-up, and all mentioned the high yield on this board.
6. I gave amounts of reactants for small scale and big scale together, so any sane person can conclude from that, that this method is infinetely upscalable, and I know of no other method which is also.
Biggest scale ever done by me was 1500 kilogram Isosafrole. Same yield.
Here's the write-up, for your convenience :

MDP2P : MethyleneDioxyPhenyl-2-Propanone (Classic Performic acid method) :

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

Isosafrole --> MDP2P via Modified Classic Performic Acid :

Materials :
Same as for ISOSAFROLE, plus :
1--minimum 500 liter stainless steel milk coolingtank, with a big-ass cooling coil in the double walls, preferable in the bottom also.
1--Mixer motor, 220 Volt, non-sparking, induction type, for :
1--Mixer propellor + axle (diam. 1.5 to 2 cm), stainless steel, diam. 40 to 60 cm.
1-- 100 liter plastic container to prepare the PerAcid mix.
and/or :
1--big-ass 80 liter dripping funnel, stainless steel, plastic or glass. Homemade is cheap.
1--1 meter cooled refluxing column, glass or stainless steel, to fix on the only opening of the milktank which is left open to the air.
5--meter heating cable, chemicals resistant, to use in milktank for the hydrolisis step with 15 % H2SO4.

Chemicals :
Reaction :
27 kg IsoSafrole, purity >/= 96 %.
99.7 kg DiChloroEthane, ClCH2CH2Cl, Industrial quality >/= 98 %.
or :
99.7 kg DiChloroMethane, CH2CL2, Industrial quality >/= 98 %.
8.3 kg SodiumBiCarbonate, NaHCO3, pure.
41.5 kg Formic Acid, HCOOH, 86 %.
25.1 kg HydrogenPeroxide, H2O2 30 %.
22.43 kg Sulfuric Acid, H2SO4 Industrial quality ~99 %.
127.07 kg water, H2O, pure.
42.4 kg Methanol, CH3OH, Industrial quality >/= 98 %.

Extraction :
To extract from 218,9 kg hydrolized Glycol/15%H2SO4/CH3OH mix :
60 liter DCM or DCE = 3 x 20 liter, Industrial quality >/= 98 %.

Method :
Here are the original figures from literature in grams, for a 27 KG batch of Iso-safrole to MDP2P :
---(all figures multiplied with: 27000 grams devided by 16.25 grams = multiply them with 1661.54 ) ---

M1. - Combine 16.25 grams [or 27 kg ] of Isosafrole with 50 ml=60 gram (1 liter DCE or DCM = 1,2 kg), [or 99.7 kg] DCE (DiChloroEthane) or DCM (Dichloromethane) plus 5 Grams [or 8.3 kg] Sodium bicarbonate (Sodium Hydrogen Carbonate : NaHCO3).
Can be made by bubbling CO2 gas in a strong soda solution (Na2CO3.10H2O ), the sparsely soluable NaHCO3 will precipitate.
M2. - Let it vigorously stirr for 2 or 3 hours, depending on the strength of your mixer [a total of 135 kg ].
This gives it time to form a pH-buffering complex which facilitates the next reaction enormously.
M3. - Seperately s.l.o.w.l.y combine (under external cooling) 25 gram [41.5 kg] 86% Formic acid and 15.1 grams [25.1 kg] 30% fresh Hydrogen Peroxide (to create Performic acid) and cool to 0 C.
Note : It is critical to cool when preparing this mixture or else it will, after sitting for 3 or 4 hrs without cooling, start boiling and nasty fumes will fill your lab and you will have to evacuate the place.
M4. - Then drip this cold Performic-acid [66.6 kg] VERY VERY slowly , into the 135 kg ISO-DCE-Sodiumbicarbonate mix, keeping temp under 40 C with external ice-bath or other means of cooling until all is in , CO2 bubbles out of the reaction mix while dripping in (and watch the temp for the following 1-2 hours, after completing dripping in, closely, so it still can not exceed 40 C).
M5. - Stir !VIGOROUSLY!, preferably with an overhead stirrer, for a total of 6(six) hours.
M6. - Stop stirring and move the whole batch in portions to a big seperatory funnel, and let it sit for one hour in there.
M7. - It will be orange-juice color DCE/pre-MDP2P(Glycol) mix at the bottom and clearish performic acid mix (H2O2/HCOOH) on top, the orange layer with the pre-MDP2P (Glycol) and DCE is heavy, so it goes fairly fast to the bottom of the funnel.
M8. - Important Note: --------------------------------------Many members have reported a switch of layers when they used DCM. Iso/DCM layer on top OR at bottom !
There is a perfectly logical explanation for this phenomenon : The one's who's cooling equipment functioned o.k. and thus kept the temperature between 36-40 Celsius will see the Glycol/DCM at the bottom after separation period, because they still have all their DCM left in the mix. The one's who were not so lucky and let the temperature get out of hand will see the orange layer at the top, due to an extensive loss of DCM which evaporated into thin air. The densities of the normal Glycol/DCM mix and the PerAcid mix lay close together, so if you evaporate too much DCM this balance is switched and suddenly the PerAcid mix is the heaviest layer, and falls to the bottom. You will notice then a light yellowish PerAcid mix at the bottom and a orange-juice coloured Glycol/DCM mix on top. This is no reason for real worry, unless you boiled most of the DCM away (not good for your health if you were in the same room (carcinogenic) AND not good for the reaction which did not have enough cooling capacity anymore in the last stage, depending on how high you overshoot the temp. Boiling temp of DCE = 83 C, DCM = 40 C , that's the reason WHY you must keep the temp under 40 C when you use DCM! And you must also do this when you use DCE !
Instructions are allways given with a reason, which is in literature expected to be common knowledge, but not here at a forum crowded with C(r)ooks (hehe) and a few real chemists.
Thought I owed the Cooks the explanation for this reason.
------------------------------------------------------------------
M9. - Seperate into a new empty container and evaporate (low-vacuumdistillation, but KEEP the TEMP under 60 C!! so use more vacuum , so go lower then 700 mbar if the temp rises too high) the DCE off and stock that recovered DCE for future use.
M10. - You should add now 180 grams [but in reality, in contradiction to the official reference, only HALF the amount necessairy!, so 90 grams = 149,5 kg] of 15% Sulfuric acid (H2SO4) [so : add 22.43 kg 99% H2SO4 to 127.07 kg water], boil it until it starts refluxing back with slight addition of 60ml=51 gram Methanol [only HALF! needed, so 25.5 gram = 42.4 kg Methanol (1L methanol=0.85 kg)] through the cooling/reflux condenser added on the distillation kettle for 2 hrs. No longer then 2 hours !!! Or you will begin to loose product-yield. You now converted the Glycol to raw MDP2P, mixed with some pollutants.
M11. - Let it cool and extract 3 times with enough DCM (or DCE), (minimum 10 reactionvolume-percent per extraction).
M12. - Combine the DCM or DCE extractions and then boil the solvent (DCM or DCE) off (in fact no vacuum needed, but if you are in a hurry:)with one or more aspirators combined or diafragm vacuumpump to get brown oil that is peppery and cardamon smell.
M13. - You get around 16 grams [26.6 kg] -dirty- MDP2P.
M14. - To get the real clean MDP2P, you will have to vacuum-distillate this dirty MDP2P-base again to get a reasonable yield of about 73-75 % (grammole-percent)= 17.8 kg clean MDP2P which should be light yellow, or if you distill exact and have no leaks to let tiny amounts of air in, and you don't let the temp go over 170 C, at ~20 mbar vacuum, it would be clear with no color.

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Note:
In weight/weight procents you get 16 / (16.25 / 100%) = 98.46 w/w % , but yield is scientifically allways given in Mole-percents, so:
(16 gram x 178.188=molecularweight MDP2P / (16.25 gram x 162.188=molweight Iso / 100%) = 2851.008 grammole / (2635.555 grammole / 100%) = 108.17 mole %.
But the effective mole % after distillation (=ultimate clean-up, no washings then necessary!) is 75%.
20 mbar x 0.01450138 = 0.29 psi, which is good enough for all distillations we work with !
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

Here are the four threads on the old board I found back again which are relevant for the classic performic:

1.

Post 107771 (missing)

(smokemouth: "LaBTOP/Gyro performic results - Sumerian", Methods Discourse)
LaBTOP-Gyro performic results - Sumerian .
2.

Post 107780 (missing)

(smokemouth: "LaBTop/Gyro's Modified Performic Questions - Synthia", Methods Discourse)
LaBTop-Gyro's Modified Performic Questions - Synthia.
3.

Post 107770 (missing)

(smokemouth: "New Performic Scale Up Question? - artech", Methods Discourse)
New Performic Scale Up Question - artech.
4.

Post 107739 (missing)

(smokemouth: "The correct way to mdp2p via performic - gyrogearloose", Methods Discourse)
The correct way to mdp2p via performic - gyrogearloose .

And this is the original Classic Performic post in the thread :

http://hive.lycaeum.org/ubb_board/Forum3/HTML/000613-3.html

NaBH4 question : solution: One Pot ! :

Classical Per-acid oxidation of Isosafrole to get Piperonylacetone (MDP2P):

(Iso.) [R]-CH=CH-CH3 ----> [R]-CH2-C(=O)-CH3 (Pip.Ac.)
R=Methylenedioxyphenyl

The PerAcid solution is made from 25 g. HCOOH (formic acid)(86% ,starting from 99% HCOOH) and 15.1 g. 30% H2O2 (hydrogen peroxide).
This sol. is added to a mixed sol. of 16.25 g. Isosafrole(>/=90%) and 1,5 g. NaHCO3 (!!) in 50 ml CH2Cl-CH2Cl at 35-40 C.
The temp. is during 6 Hrs. mixing regularaly checked and kept within 35-40 C.
The solvent is evaporated (vacuum, keep TEMP! UNDER! 60 C.!).
Residue is boiled with 180 g. 15% H2SO4 for 2 Hrs.
Extraction with 3 x 100 ml.CHCl3, wash with water,dry over MgSO4 and evaporation of the solvent gives a brown oil (purity >/=90%).
Supplemental purifying by Kughelruhr destillation (~70 C, 0,2 Torr) gives 70-75% yield of MDP2P (>/= 95% pure!)

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

And this is the latest info from Ritter, who by the way posted this method first, then Beagle_boy , then me, then Gyrogearloose, so this method needed 3 times posting to get the attention needed, so lets call it from now on the Classic Performic, to avoid any misunderstandings:

Ritter
(Stranger)
06-20-00 14:26
Re: LabTop modified performic method?

The reaction runs best as described in my writeup! Adding carbonate to formic/peroxide first would surely lead to a nasty volcano and would not help any. Carbon Dioxide is emitted as performic is slowly added to alkene/carbonate solution. As far as advances are concerned a few things have been realized. Extremely vigourous stirring, such as that produced by a mechanical stirring rig, seems to increase yields. If a considerable amount of isoalkene is recovered during vacuum distillation an easy solution is to add more performic acid mix to rxn. This is usually an indicator that the peroxide used has degraded somewhat below 30%.
With this MDP2P you proceed to make :


WISDOMwillWIN

Ritter

  • Guest
Re: Medium scale performic
« Reply #7 on: April 15, 2001, 06:37:00 PM »
Ahh, the infamous modified" performic returns to the table.

I must say LaBtop, you have quite a remarkable ability of recalling who said what over these years.

Re: NaHCO3 vs Na2CO3 in modified performic
Here's the deal.  First off, SWIM never used bicarb in his past experiments for one reason.  When he ran the rxn. using carbonate the yield of the intermediate monoformyl glycol was always produced in exactly quantitative yield.  By this he means that after running rxn with 1 Mol (162g) isoalkene, sepping off organics and rotovapping, the residue always weighed 238g.  That happens to be the exact mass of 1mol of the intermediate meaning that this reaction actually ran dam near quantitatively.  In all honesty, SWIM has never seen another rxn of any type which produced a 97-100% yield everytime.

Swim always thought that the yield killing step was the acid hydrolysis, however this was proven to be completely untrue when the crude ketone from the acid hydrolysis was distilled using the latest evaporator.  Less than 10 percent of the product charred into that nasty ass black tar during the distillation with this beautiful piece of equipment as compared to 20-30% when standard vacuum distillation techniques were used.

So, in a nutshell, if you can distill your crude ketone produced using my rxn. with the latest evaporator prepare to see the most amazing yields possible from a performic reaction.(85-90%)

If you only have regular vac. distilling equipment 75% is a definite unless you really overheat your still pot.



baalchemist

  • Guest
Re: Medium scale performic
« Reply #8 on: April 16, 2001, 01:13:00 AM »
Baals notes on this( from original thread mentioned above) reflect a 38%-H2O2 being used with 86%-Formic intead of
30%-H2O2. Was that a typo on my part?  I have always used 35% with an add'l 3%-volume added to compensate. Nonetheless its been working excellent all this time despite its slight variances from the original reaction details posted by LabTop on the old forum. However it does substantiate the fact that even some small parameters of error will not substantially affect yields. 2 parameters that definately cant be compromised, is the 2 hour hydrolysis time and using weakened H2O2 (less than 30%) as Ritter stated. It possibly could be done with 25%-H2O2, if a 98%-Formic acid was used. In theory at least the excess H2O would be taken up into the Formic, decreasing its %. On a side note, Baal will measure the specific density of the
Performic mixture next time and post its value for those
into density measurements like SWIMyself. Hats off once again to LabTop and Ritter(and whatever happened to Beagle Boy?)for the added weapon to Baals OTC arsenal
(& NO ACETONE!) 8)

blue

  • Guest
Re: Medium scale performic
« Reply #9 on: April 24, 2001, 11:38:00 AM »
Great work guys! I never had a serious look at this method before, wow! Couple quik questions if you don't mind, just to address the disparities between your two methods.

LT uses cooling to maintain very specific temp during performic rxn. Ball uses DCM as his only temp control and makes no mention of it subsequently, yet allows rxn to run 18 additional hours. is the 18 extra hours to compensate for lack of temperature control in Baals method?

the other disparity is in the hydrolysis, LT adds MeOH. Is it's sole function to lower the temperature of reflux?

Baals method maintains temp control of 75C but that is below the temp at which his alcohol free hydrolysis mixture will reflux.Is the MeOH not necessary?  Is reflux not necessary?

Thanks in advance  :)


as in cobalt

OChem

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Re: Medium scale performic
« Reply #10 on: April 30, 2001, 07:47:00 AM »
This might be a retarded question but.....If what other people has said is true (foxy2) and you can use acetic acid instead of formic....why would you use formic acid?? Is there an advantage?
SWIM was planning on doing the prefomic with GAA as her first dream, is there anything she should know?


Idle hands.......

goiterjoe

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Re: Medium scale performic
« Reply #11 on: April 30, 2001, 05:10:00 PM »
the performic can be done in a third of the time of the peracetic.  the peracetic acid requires sulfuric acid as a catalyst to make it, and the sulfuric has to be neutralized with an acetate salt to prevent it from causing byproducts in the reaction.  the peracetic has to be formed overnight, while the performic can be formed almost instantaneously.  the performic addition also runs faster than the peracetic.


If pacman influenced us, we'd glide around dark rooms eating pills and listen to repetitive music.

baalchemist

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Re: Medium scale performic
« Reply #12 on: May 01, 2001, 05:41:00 PM »
SWIM uses Formic by choice, personal favorite. GAA works if you have no access to Formic, but has its disadvantages as stated above.

Semtexium

  • Guest
Re: Medium scale performic
« Reply #13 on: May 13, 2001, 11:59:00 AM »
Also the peracetic can produce acetone peroxide which is a fairly unstable/sensitive high explosive.  And the freaky part is where it shows up, it comes over while one distills the ketone, your condenser's insides are coated with these really nice looking xtals that you have to filter out of your ketone distillate.  But I know of no one that has had any problems because of the peroxides formed, and the resultant ketone from the peracetic has been aminated with success time and time again.  I just thought that the danger of the explosive forming should be brought to light so you can more acuratly look at the proceedures and judge for yourself which if any your comfortable with...  ;)


::)  ::)