Monday, November 17th 2019
Bismuth Tetroxide, Bi2O4, hydrated with one or two molecules of water, is formed when sodium bismuthate is decomposed with nitric acid; the anhydrous substance has not been obtained by this method, as oxygen is lost when water is removed.
Updated Synthesis List
  1. Potassium chlorochromate 1390
  2. Ammonium Pentaperoxodichromate 1392
  3. Chromium (III) Glycinate 1382
  4. Trichlorotriamminechromium 1381 from Diperoxotriamminechromium (IV) 1392
  5. Trichlorotriethanolochromium 1380
  6. Potassium Iron(III) Sulfide 1507
  7. Hexaamminecobalt (III) Chloride 1531
  8. Chloropentaamminecobalt (III) Chloride 1532
  9. Chromium Trioxide
  10. Sodium Dithionite
  11. Uranium (IV) Oxalate
Thursday, November 14th, 2019
Structure of Silicomolybdic Acid
Preparation of Sodium Silicomolybdate 1729-1730
12Na2MoO4 + Na2SiO3 + +22HNO3 → 22NaNO3 + 2Na2SiO40 

PROTOCOL FOR PMC HOME LAB SYNTHESIS

  1. A solution of 5 grams of sodium molybdate in 20 mL of hot water is prepared. 
    1. Conversion factor = 5/289.096 = 0.017295292913
  2. 4.32 mL of concentrated nitric acid is diluted down to 6.05 mL total volume. This is rapidly added in portions with stirring.
  3. Next 0.48 grams of sodium monosilicate is slowly added to the solution with stirring.
    1. Several drops of sodium silicate are boiled for several minutes in 1.6 grams NaOH dissolved in 20 mL of water. 

PROTOCOL FROM HANDBOOK FOR INORGANIC CHEMISTRY

  1. 172 grams MoO3 is added in portions over the course of 10-15 minutes to a solution of 60 grams NaOH in 400 mL of boiling water.
    1. Molar mass of MoO3 = 143.95 grams per mole.
      1. 172 grams of molybdenum trioxide = 1.194859326 moles
    2. Molar mass of Na2MoO4•2H2O = 241.95 grams per mole
      1. 1.194859326 moles of sodium molybdate = 289.096 grams ​​​​
    3. Molar mass of NaOH = 39.9971 grams per mole
      1. 60 grams of sodium hydroxide = 1.500 moles
  2. When this is fully dissolved interrupt the boiling to add 500 mL of water to the mixture. 
  3. Next 250 mL of concentrated nitric acid (d. 1.39) diluted down to a volume of 350 mL is rapidly added in portions with stirring.
  4. Once all of the nitric acid is added the sodium silicate is added immediately afterward in a thin stream with constant stirring.
    1. 28 grams of commercial crystalline sodium silicate nonahydrate is dissolved in 125 mL of 2N NaOH and then boiled for 10-15 minutes to effect conversion to the monosilicate.
  5. The solid compound cannot be isolated but the solution (whose acidity must be maintained) can be used as-is to precipitate cesium and rubidium.
Tuesday, November 12th, 2019
Preparation of Chromium(III) Glycinate 1382
  1. An aqueous solution of one mole of chromium(III) chloride hexahydrate and 3 moles of glycine is prepared.
  2. The solution is boiled and 3 moles of sodium hydroxide is gradually added. 
  3. This produces a deep red solution from which a violet compound precipitates. 
  4. The violet compound is filtered off while the solution is still hot. 
  5. The filtrate, after cooling and standing in vacuum over sulfuric acid, deposits more of the violet crystals along with larger red crystals. 
  6. The crystals are suction filtered and dried. 
  7. The heavier red crystals of chromium(III) glycinate are separated from the lighter violet crystals of basic chromium(III) glycinate by slurrying with alcohol. 
    1. Both compounds are sparingly soluble in water and insoluble in organic solvents. 

Preparation of Chromium(III) Alaninate

  1. As above except if the solution is allowed to take place in a concentrated solution then chromium(III) alaninate separates out and the basic chromium(III) alaninate is obtained by evaporation of the solution. 

Preparation of Sodium Phosphotungstate 1720

  1. A solution of 10 grams of sodium tungstate dihydrate and 5 grams of disodium hydrogen phosphate dodecahydrate in 16 mL of water are evaporated until a surface skin of crystals forms.
  2. 15 mL of 24% HCl (d. 1.12 g/mL) is added with stirring. A precipitate forms momentarily but then redissolves completely.
    1. ​​​​​​​(31.5)(x)=(24)(15)
    2. x=11.428 mL of conc HCl diluted to 15 mL
  3. The solution is evaporated on a steam bath until a crystal skin begins to form.
  4. The product is recrystallized from boiling water. 
Monday, November 11th, 2019
Preparation of Chromium Trioxide from Ammonium Dichromate
  1. Ammonium Dichromate = 252.07 grams per mole 
    1. Solubility: 18.2 g/100ml (0 °C), 35.6 g/100ml (20 °C), 40 g/100ml (25 °C), 156 g/100ml (100 °C)
  2. Sodium Hydroxide = 39.9971 grams per mole
  3. Ammonia = 17.031 grams per mole
  4. Water = 18.01528 grams per mole
  5. Sodium Chromate = 161.97 grams per mole
    1. Solubility: 31.8 g/100 mL (0 °C), 84.5 g/100 mL (25 °C), 126.7 g/100 mL (100 °C)
  6. Sodium Dichromate = 261.97 grams per mole
    1. Solubility: 73 g/100 mL at 25 °C
  7. Sulfuric Acid = 98.079 grams per mole
  8. Chromium Trioxide = 99.993 grams per mole
  9. Potassium Chromate = 194.189 grams per mole
    1. Solubility (g/100mL): 62.9 g/100 mL (20 °C), 75.1 g/100 mL (80 °C), 79.2 g/100 mL (100 °C)
  10. Potassium Dichromate = 294.185 grams per mole
    1. Solubility (g/100mL): 4.9 g/100 mL (0 °C), 13 g/100 mL (20 °C), 102 g/100 mL (100 °C)

(NH4)2Cr2O7 + 4NaOH → 2NH3 + 3H2O + 2Na2CrO4

  1. Dissolve as much of 48.11 grams of ammonium dichromate in 95 mL of water as possible.  
    1. 100 grams of sodium dichromate is 0.3817230 moles. Cut that amount in half due to inventory limitations.
    2. 0.1908615‬ moles of ammonium dichromate is 48.11 grams.
  2. Add dropwise with stirring a solution of 30.54 grams of NaOH dissolved in 30 mL of water. 
    1. 0.763446‬‬ moles of NaOH = 30.54 grams
  3. ​​​​​​​Once all of the aqueous sodium hydroxide has been added the solution is heated to boiling and it is allowed to boil for a short time. More water is added if needed to keep the volume at 125 mL.
  4. Once all of the ammonium dichromate has been converted to sodium chromate the solution is allowed to cool to room temperature.
  5. Concentrated sulfuric acid is added dropwise with stirring until a slight lasting precipitate of chromium trioxide is formed. A little more than 100 mL will be necessary as some of the sulfuric acid is consumed converting the sodium chromate to sodium dichromate. 
  6. The mixture is then cooled in salted ice water for 30+ minutes.
  7. 100 mL of concentrated sulfuric acid is then added dropwise to the chilled solution in order to fully precipitate chromium trioxide. 
  1. PROTOCOL FROM PREPCHEM.COM
  2. 100 grams of sodium dichromate are dissolved in 250 ml of water and the obtained solution is filtered.
  3. 200 ml of concentrated sulfuric acid are dropwise added with constant stirring until a slight permanent precipitate of chromium trioxide is formed.
  4. The mixture is cooled for half an hour or longer, then slowly, while stirring, 200 ml of concentrated sulfuric acid are added dropwise.
  5. The reaction mixture is left to stand over night in order that the crystal meal may become somewhat coarser. The larger crystals (and purer) of chromium trioxide could be obtained by heating the solution with crystal meal with stirring to 100° C and allowing to cool slowly. If this process is repeated once or twice, a more satisfactory product will be obtained.
  6. The obtained crystals of chromium trioxide are filtered with a Buchner funnel with a sintered glass disc instead of the usual paper filter (chromium trioxide is a strong oxidizing agent and will oxidize organic material).  
  7. Drain the crystals completely and press the surface.
  8. Treat with 15 ml of concentrated (65-70%) nitric acid. The nitric acid is removed by suction and the operation is repeated twice with 10 ml of nitric acid each time. 
  9. Finally, the red crystals of chromium trioxide are dried by suction as much as possible, transferred in a dry evaporating dish and by gentle heating the remaining nitric acid is removed. Dried product is stored in a stoppered bottle. Yield is 60%.

Friday, November 8th, 2019

Updated List of Possible Video Syntheses

  1. Potassium chlorochromate 1390
  2. Ammonium Pentaperoxodichromate 1392
  3. Chromium (III) Glycinate 1382
  4. Trichlorotriamminechromium 1381 from Diperoxotriamminechromium (IV) 1392
  5. Trichlorotriethanolochromium 1380
  6. Potassium Iron(III) Sulfide 1507
  7. Hexaamminecobalt (III) Chloride 1531
  8. Chloropentaamminecobalt (III) Chloride 1532
  9. Chromium Trioxide
  10. 12-Tungstic Acid-1-Phosphates 1720 (aka Sodium Phosphotungstate)
  11. 12-Molybdic Acid-1-Silicates 1729 (aka Sodium Silicomolybate)
  12. Sodium Dithionite
  13. Uranium (IV) Oxalate

Wednesday, November 6th, 2019

I am working on improving my crystal growing and photographing techniques. I set up the desiccator with 3A molecular sieves like normal and then after the solutions on their watch glasses were placed in there and the lid closed up on it I put a heater right next to it and had it blow onto the desiccator. That raised the temperature in the desiccator significantly which drove complete evaporation of the droplets and the quicker formation of still very well formed crystals. I then had the heater blow directly onto the watch glass as I photographed the crystals. This produced GREAT crystal films for the solutions but there still wasn't enough heat to keep the crystal films from rapidly absorbing water. Stronger heating while taking the pictures is needed.

I need another good compound to do for the channel. I am going to work on getting that TLC protocol for indole alkaloids ready for filming. That will probably take a while. It's pretty involved. I bought a glass cutter to make my TLC plates stretch further. I am also going to need to make up a modified Ehrlichs's Reagent to visualize the spots and that is going to take some work all by itself. In the meantime I need to come up with another good compound I can film me making. Trying to find a good exotic inorganic that I haven't done yet but that I am able to do with what I have. 

I was thinking of maybe trying to see if barium iridate will form the same acetyl complex that barium ruthenate does. That could be cool. And if I make some pyridine I can make up a cool cobalt complex. I could REALLY use a stir plate!!! But none of that will be ready to do today so the next full length video is going to be some transition metal complex. Haven't quite decided which one to do but these are the candidates:

  1. Cesium dichromate or Rubidium dichromate 1389
  2. Potassium chlorochromate 1390
  3. Ammonium Pentaperoxodichromate 1392
  4. Chromium (III) Glycinate 1382
  5. Trichlorotriamminechromium 1381 from Diperoxotriamminechromium (IV) 1392
  6. Trichlorotriethanolochromium 1380
  7. Potassium Iron(III) Sulfide 1507
  8. Hexaamminecobalt (III) Chloride 1531
  9. Chloropentaamminecobalt (III) Chloride 1532
  10. Chromium Trioxide

Monday, October 28, 2019

To a stirred solution of 717.8 g of a 32% hydrochloric acid solution in a 3-necked 2 liter flask was added 615.42 g of powdered sodium hypophosphite. The temperature of the solution rose about 2° C. Water was removed from the stirred reaction mixture by reduced pressure distillation at a temperature of about 55°C ±7° C at a pressure of 44-72 mmHg until a hypophosphorous acid concentration of about 80 wt% was obtained. After cooling to room temperature, sodium chloride that had precipitated was filtered from the reaction mixture. The filter cake was washed twice with 32 wt % hydrochloric acid. https://erowid.org/archive/rhodium/chemistry/hypophosphorus.html

  1. Density of 32% HCl = 1.161 grams per mL at 25 oC
  2. Volume of 717.8 grams 32% HCl at 25 oC = 618.26 mL
  3. 615.42 grams of sodium hypophosphite = 6.9942 moles
  4. Molar Mass of HCl = 36.46 grams per mole
  5. 32% 717.8 = 229.696 grams HCl = 6.299 moles

Friday, October 25, 2019

Beginning the testing of the EnviroKlenz air purifier today. 

Wednesday, October 23, 2019

Properties of Diethylamine

  1. Molar Mass = 73.139 grams / mole
    1. Molar Mass of HCl Salt = 109.6 grams / mole
  2. Appearance = Colorless Liquid (brown if impure)
  3. Scent = Strong ammonia-like smell and/or fishy odor
  4. Melting Point = -49.80 oC
  5. Boiling Point = 54.8 to 56.4 oC
  6. Density = 0.7074 grams / mL 
  7. Solubility in Water = Miscible
  8. Vapor Pressure = 24.2 - 97.5 kPa
  9. Flash Point = −23 °C (substance is flammable)

"Diethylamine (DEA) is distilled off and is collected in an excess of HCl. The solution of DEA HCl is then evaporated to dryness and the dry salt gently warmed with 40% NaOH solution yielding crude DEA which is purified by distillation yielding 75% of final product with boiling point 55-56° C." - Diethylamine Synthesis Protocol on Prepchem.com https://www.prepchem.com/synthesis-of-diethylamine/

Sunday, October 20, 2019

Freezing Points of Various Compounds

  1. Glacial Acetic Acid = 61.88 oF, 16.6 oC
  2. Dimethyl Sulfoxide = 66.2 oF, 19 oC
  3. Glycerol = 64.04 oF, 17.8 oC

Friday, October 18, 2019

"An aqueous solution of three parts of CdSO* • 8/3 H a O and four parts of KI is evaporated to dryness and extracted with warm absolute alcohol. The Cdl 3 crystallizes in colorless lamellae upon cooling of the solution." Handbook of Preparative Inorganic Chemistry, 2nd Edition, Volume 2, page 1097

Thursday, October 17, 2019

Another method, used especially for diiodides, involves heating the metal with HgX2: Tm + HgI2 → TmI2 + Hg 

Praseodymium and terbium form higher oxides, of which a number of phases are known between Ln2O3 and LnO2. Ignition of praseodymium nitrate leads to Pr2O3 but further heating in an oxygen atmosphere gives Pr6O11 or even PrO2; terbium similarly yields Tb4O7 and TbO2

Hard-Soft Acid-Base Theory: https://en.wikipedia.org/wiki/HSAB_theory

Thursday, October 10, 2019

PrO1.83 https://en.wikipedia.org/wiki/Praseodymium_(III,IV)_oxide

Although usually trivalent, ytterbium readily forms divalent compounds. This behavior is unusual for lanthanides, which almost exclusively form compounds with an oxidation state of +3. The +2 state has a valence electron configuration of 4f14 because the fully filled f-shell gives more stability. The yellow-green ytterbium(II) ion is a very strong reducing agent and decomposes water, releasing hydrogen gas, and thus only the colorless ytterbium(III) ion occurs in aqueous solution

Samarium and thulium also behave this way in the +2 state, but europium(II) is stable in aqueous solution.

Ytterbium metal behaves similarly to europium metal and the alkaline earth metals, dissolving in ammonia to form blue electride salts.

Friday, October 4, 2019

Free hypophosphorous acid, H3PO2, is prepared by acidifying aqueous solutions of hypophosphite ions, H2PO2-. For example, the solution remaining when phosphine is prepared from the reaction of white phosphorus and a base contains the H2PO2- ion. If barium hydroxide, Ba(OH)2, is used as the base and the solution is acidified with sulfuric acid, barium sulfate, precipitates and an aqueous solution of hypophosphorous acid results.

Ba2+ + 2 H2PO2- + 2 H3O+ + SO42- => BaSO4 + 2 H3PO2 + 2 H2O

The pure acid cannot be isolated merely by evaporating the water, however, because of the easy oxidation of the hypophosphorous acid to phosphoric acids (and elemental phosphorus) and its disproportionation to phosphine and phosphorous acid. The pure acid can be obtained by extraction of its aqueous solution by diethyl ether. Pure hypophosphorous acid forms white crystals that melt at 26.5° C. The electronic structure of hypophosphorous acid is such that it has only one hydrogen atom bound to oxygen, and thus it is a monoprotic oxyacid. It is a weak acid and forms only one series of salts, the hypophosphites. Hydrated sodium hypophosphite, NaH2PO2×H2O, is used as an industrial reducing agent, particularly for the electroless plating of nickel onto metals and nonmetals. https://erowid.org/archive/rhodium/chemistry/hypophosphorus.html

Video Ideo (Synthesis of Mexamine from Melatonin): 14g freebase melatonin was suspended in 115ml xylene. 10g NaOH (lye) and heated to 105c for two hours and cooled with 175ml water. Filter excess lye and newly formed sodium acetate and add 250ml hydrochloric acid. Remove volatiles with vacuum and freebase the resulting crystals with ammonium hydroxide solution yielding 10g 5-MeO-tryptamine.  https://www.reddit.com/r/TheeHive/comments/4tptum/5meomet_synth_making_melatonin_more_useful/

Possible to Use one of these TLC systems for Mexamine? https://www.unodc.org/unodc/en/data-and-analysis/bulletin/bulletin_1969-01-01_1_page005.html

Thursday, October 3, 2019

Ketone-catalyzed decarboxylation, as described by Drone #342:
Decarboxylation is accomplished by mixing about 80 g tryptophan in 250 mL of high-boiling solvent (xylene, DMSO, cyclohexanol, etc.), adding a dash of a ketone (I like 5 g of cyclohexanone, but a couple grams of MEK works reasonably well), heat it to around 150 deg, and when evolution of CO2 ceases/solution is clear, the reaction is complete. This takes anywhere from 1.5 to 4 hours. After this is over, the solvent is boiled off (or at least greatly reduced in volume), and the residue is dissolved in DCM. This is washed with a 5% NaHCO3 solution, then a distilled water solution, then the DCM layer is separated off, dried with MgSO4, and the DCM is boiled off. You now have reasonably pure tryptamine. https://erowid.org/archive/rhodium/chemistry/tryptophan.html

Sunday, September 28, 2019

Prep of cerium oxalate http://www.prepchem.com/synthesis-of-cerous-oxalate/

Prep of cerium dioxide http://www.prepchem.com/synthesis-of-cerium-dioxide/

Synthesis of benzaldehyde http://www.prepchem.com/synthesis-of-benzaldehyde/


https://openarchive.ki.se/xmlui/bitstream/handle/10616/37793/thesis.pdf?sequence=1 page 12
Methyl Anthranilate Synthesis Protocol to be Adapted for Ethyl Anthranilate: To the round bottom flask fitted with reflux condenser, which is protected from moisture with a calcium chloride tube, 7 g of anthranilic acid are suspended in 50 ml of dry methyl alcohol. Dry hydrogen chloride is passed until the solution is saturated and becomes hot, then the reaction mixture is refluxed for one hour. When the reaction is complete the solution is cooled and methyl anthranilate hydrochloride crystallizes. The mixture is diluted with 200 ml of water and made alkaline by the solution of sodium carbonate. The oily methyl anthranilate is extracted with ether and the extract washed with 5 % sodium carbonate solution, and then with water. The extract is dried over sodium sulfate and evaporated to small bulk. The distillation in vacuum and collecting fraction boiling at 135° C (15 mm of Hg), yields a crystalline mass melting at 24.5° C.
Tryptamine from Tryptophan: https://erowid.org/archive/rhodium/chemistry/tryptophan.html

Thursday, September 19, 2019

I ordered 100 grams of diethylamine HCl after all. I decided in the end to go with it because I really want to do some of the experiments I've read about using lanthanide diiodides in secondary amines. The papers I've found use diisopropylamine but that stuff is $40 for something like 30 mLs! I will be able to generate twice as much amine for half the price if I can make it work with diethylamine instead of diisopropylamine. Eventually I'd like to try both. But for now I will try the diethylamine and see if it works. To my knowledge no one has tried this yet (not that I can find in the literature anyways; I'm sure it's been done before).

I ordered 100 grams of diethylamine HCl after all. I decided in the end to go with it because I really want to do some of the experiments I've read about using lanthanide diiodides in secondary amines. The papers I've found use diisopropylamine but that stuff is $40 for something like 30 mLs! I will be able to generate twice as much amine for half the price if I can make it work with diethylamine instead of diisopropylamine. Eventually I'd like to try both. But for now I will try the diethylamine and see if it works. To my knowledge no one has tried this yet (not that I can find in the literature anyways; I'm sure it's been done before).

That stone is STILL strongly colored! It's been sitting out for several days now and it is even more strongly colored now than it was to begin with! But for spilling that reaction mixture I would never have dreamed that stuff would do this to stone. You can see that even some of the crystals have taken up the color. I'm sure it's just a surface coating but I have no idea what is bonding it to the quartz. And using other amino acids doesn't work; I've already tried. Only tryptophan does this out of the ones that I've checked so far. How freaking cool is that?

As I tinker around with several different experiments trying to make them video-worthy I was thinking of simple, easy things that I could do that would still be semi-original but that people would be interested in. I found a paper where the authors did an extraction of harmala alkaloids from passion flowers that I thought would be really cool. I have some ground up Syrian Rue that I could extract it from which should give me a decent yield (I don't have enough material to do passion flower unfortunately). However, it would all be done the same and the same method could be applied to any alkaloid extraction since it's very generalized. 

I just found a 52 page thesis called "The Synthesis of Heterocycles from Anthranilic Acid and its Derivatives" on Google!! It's loaded with all kinds of goodies; tons of information on anthranilic acid and its reactions. It gives a general outline on how to do the reaction between anthranilic acid and chloroacetic acid (a very general outline) but it might just be enough to work from. The same paper also gave some great info on how to get esterification reactions to dominate over N-alkylations so that should help in my ethyl anthranilate synthesis as well. I'll tell you what these undergrad and grad level theses are really turning out to be super helpful!

Tuesday, September 17, 2019

Today I am going to do a full test of the tryptaldehyde synthesis. If it works there will be a video on it in the near future. I don't see why it wouldn't work at this point. I'd also like to try the esterification reaction with some of the anthranilic acid I made to make a small amount of ethyl anthranilate to test the reaction before I film it. Now would be a good time to have some too because the mosquitoes are a real pain in the ass in the evening around here.

Monday, September 16, 2019

I just figured out how to separate out the tryptaldehyde from the reaction mixture!!! As it turns out I don't need to use a solvent based extraction at all! The paper that I am working from references an old practical organic textbook from 1973 for their method of separating out the aldehyde and I just managed to get a copy of it (Vogel's Textbook of Practical Organic Chemistry, 3rd Edition pgs 331-332). This is so neat they use an excess of a saturated water/ethanol solution of sodium bisulfite to precipitate out the aldehyde. This is an equilibrium reaction so once filtered off the free aldehyde is easily regenerated by reaction of the solid with aqueous sodium carbonate or hydrochloric acid to remove bisulfite ion and shift the equilibrium back to the left. What a kick ass cool trick!!!

I've decided not to do the video on diethylamine after all. The reason being it's just too readily available and too cheap to really make it worthwhile. If I was to get diethylaniline and make diethylamine from that it would cost me $40 with shipping and at best I could expect to make about 20-30 mL of diethylamine. However, you can just buy diethylamine hydrochloride on eBay and 100 grams is $19.90 with free shipping. That being the case why would you need to make it out of OTC stuff? You can just buy it for cheap.

My anthranilic acid video is now my most viewed video on BitChute and it grew in views more than twice as fast on YouTube as any other video that I've put out. The first Reagent Test video is still number one in its steady growth in views and the Dilithium Telluride clusterfuck video is still my most viewed video of all time but the anthranilic acid one is the best performing one even if it hasn't racked up as many views as those others. The tryptaldehyde video should be another good one. Succinimide would also be good if I could get it to fucking work WITHOUT cracking any more round bottom flasks!

Thursday, September 12, 2019

So I discovered this totally by accident. If you pour the reaction products of tryptophan, potassium ferricyanide, and potassium hydroxide (indole-3-acetaldehyde is one and potassium ferrocyanide is another) out onto stone and leave it in the shade for a while it turns the stone blue/green. It doesn't wash off with water (at least, not easily). It doesn't stain very pure quartz crystals well but it adheres to every kind of stone I've tried it on thus far. I have no idea what it is but it doesn't work with other amino acids, tryptophan and potassium ferrocyanide, indole-3-acetaldehyde dinitrophenylhydrazone, or potassium ferricyanide, Brady's Reagent and ferrocyanide mixture. Only the reaction product of that particular reaction does it. And it won't do it in the sun but once you put it in the shade (even if you've rinsed it off first) then the color changes. However, if you rinse it first then the color isn't as vivid. I found all of this out just by playing with this thing. It's pretty neat. Wish I knew what it was.

Wednesday, September 11, 2019

I am glad that I decided to film the anthranilic acid synthesis again. I knew that trying to do it with nothing but a Wikipedia entry and a bare bones synthesis protocol would be a challenge but I managed to screw it up somewhere along the line. But that's alright. I am pretty sure I've identified all the errors so I am going to try it again today. I think the thing to do is to control the temperature and pH more carefully and change the way things are added together. The protocol literally reads as "put everything in a beaker and dissolve it" as the first step. I thought that seemed kind of weird but I went with it anyways and that's when things started getting wonky. I am still not sure what product I actually got. It could be anthranilic acid and the yield just sucks. But during the synthesis I could smell ammonia and I REALLY shouldn't have been able to smell ammonia! The only place ammonia could have come from is the amino group on the benzene ring. How the holy hell that was removed off benzoic acid I have no idea but there you have it.

I finally broke down and watched ChemPlayer's video on doing this reaction and I confirmed a few suspicions and picked up a few tips. I hate to do that because I don't want to just repeat what someone else does. So I am going to stick with the prepchem protocol but with a few minor modifications. This should do the trick. Fingers crossed!!!

Tuesday, September 10, 2019

Succinimide failed. I'm beginning to think I'm losing my touch.  I am going to try doing the anthranilic acid synthesis today. Hopefully that one works better (third times the charm). I know why succinimide failed (I think). I am going to dry the ammonium succinate more thoroughly, come up with a better apparatus, and then try again later. I really hope that SOMETHING works soon!

  1. 20 g of finely powdered phthalimide and 40 g of sodium hydroxide are dissolved together in 140 ml of water, the solution being cooled during the operation.
  2. The solution is agitated, and 200 g of a 5% solution of sodium hypochlorite run in.
  3. When all is added, the solution is warmed for a few minutes at 80° C to complete the reaction;
  4. it is then cooled and neutralised exactly with hydrochloric acid (or sulphuric acid).
  5. An excess of strong acetic acid is added to precipitate the anthranilic acid, which is filtered off and washed with water.
  6. Any anthranilic acid remaining in the filtrate is precipitated as copper anthranilate by the addition of a saturated solution of copper(II) acetate.
  7. After standing for some time the precipitate is filtered off and suspended in a small quantity of warm water, while a current of hydrogen sulfide is passed into the suspension.
  8. The copper sulphide formed is filtered off, and anthranilic acid recovered from the filtrate by concentration on a water bath.
  9. It may be recrystallised from hot water. Total yield 85%, m.p. 145° C.

Wednesday, September 4, 2019

OK the synthesis of potassium bromate/bromide is not turning out to be great video material. I think that every little thing that could go wrong did. I got a good yield of potassium bromate (21.4 grams before drying which is about what I got the last time I did this) and I might take that footage and compile a smaller video of just that later on. Looking back at the videos I've done people seemed to like the ones where I was doing something for the first time the most. So I've decided to switch gears and while I work on salvaging the potassium bromide I am going to film a synthesis I have never done before and I think it's one that people will like. I am going to do the synthesis of succinimide from succinic acid. As an added bonus I can take that succinic acid product and convert it into N-bromosuccinimide in a future video (the process look pretty simple).

  1. 20 g of succinic acid are dissolved in a small quantity, of water in a basin,
  2. and the solution neutralised with ammonia.
  3. The solution is boiled to expel excess of ammonia,
  4. after which a further 20 g of succinic acid dissolved in water are added.
  5. The solution is evaporated to complete dryness on a water bath;
  6. the dry residue is transferred to a retort and heated quickly with a large luminous flame.
  7. The sublimate of succinimide is recrystallised from pure acetone
    1. Yield 70%, colourless rhombic plates; m.p. 126° C; b.p. 288° C. 
    2. http://www.prepchem.com/synthesis-of-succinimide/

Preparation of Succinimide

.

Monday, September 2, 2019

Synthesis of Chromium Trioxide http://www.prepchem.com/synthesis-of-chromium-trioxide/

Conversion of Chromium Trioxide to Ammonium Chromate https://www.youtube.com/watch?v=VO9ovvbHS-Q

Synthesis of Quinone (1,2-benzoquinone) from Hydroquinone = http://www.prepchem.com/synthesis-of-p-benzoquinone/

Saturday, August 31, 2019

Synthesis of Anthranilic Acid http://www.prepchem.com/synthesis-of-anthranilic-acid/

Synthesis of Potassium Phthalimide http://www.prepchem.com/synthesis-of-potassium-phthalimide/

Synthesis of Nitromethane http://www.prepchem.com/synthesis-of-nitromethane/

Henry Reaction (combination of nitroalkanes and aldehydes/ketones to form beta-nitro alcohols) https://en.wikipedia.org/wiki/Henry_reaction

Synthesis of Iodine Pentoxide (Iodic Anhydride) http://www.prepchem.com/synthesis-of-iodine-pentoxide/

Amine Alkylation https://en.wikipedia.org/wiki/Amine_alkylation

Synthesis of Succinimide http://www.prepchem.com/synthesis-of-succinimide/

Cadmium(II) polymers with anthranilic acid derivatives (n-carboxymethyl anthranilic acid aka n-phenylglycine-o-carboxylic acid) https://www.sciencedirect.com/science/article/pii/S0020169305003737

The tetrahydrofuran and phthalic anhydride arrived yesterday!!! I am SO excited! I finally managed to find a source for anhydrous tetrahydrofuran. Thank the magic sky daddy that it can be recycled out of any experiment I use it in! Just 120 mL was $72!!! But it's highly pure and anhydrous so I can use it directly in the lanthanide diiodide experiments without having to dry it over anything more than a small piece of metallic sodium. I went ahead and got some phthalimide as well which is only one step away from anthranilic acid and will probably yield a purer product. However, I am still going to demonstrate the conversion of phthalic anhydride into phthalimide and having the phthalic anhydride is good because that gives me a pure product to compare to what I get when I attempt the oxidation of naphthalene. 

Friday, August 30, 2019

I finished cleaning up the sodium metal. In the end I was able to get one giant lump and a couple of smaller spheres which got lost in the goop left after cleaning the metal and so ended up in the trench in the end along with myriad tiny pieces of sodium metal. It was pretty cool since the large amount of mineral oil kept many of them from reacting with the water for quite a long time. I cleaned the metal by heating it up in mineral oil, melting it down, breaking it up into tiny spheres, changing out the mineral oil a couple times, and finally by adding small amounts of azeotropic isopropanol to the hot oil with stirring. The alcohol breaks up the crud enough to allow the beads of sodium to conglomerate into a single large piece. Then I just let it cool down, skewered it with a glass rod, and then transferred it to a jelly jar with mineral oil. Tomorrow when I have more time after work I will cut this into small pieces and then I will be ready to keep THF (and any other ethereal solvent) bone dry and peroxide free for the foreseeable future. YAY!  Now I can go buy some starter fluid and distill some diethyl ether and actually keep it around instead of having to distill it every damn time I need some! 

Synthesis of Acetaldehyde http://www.prepchem.com/synthesis-of-acetaldehyde/ 

Synthesis of Potassium Chlorochromate http://www.prepchem.com/synthesis-of-potassium-chlorochromate/

Synthesis of Potassium Phthalimide http://www.prepchem.com/synthesis-of-potassium-phthalimide/

Synthesis of Phthalimide http://www.prepchem.com/synthesis-of-phthalimide/

Synthesis of Succinic Anhydride http://www.prepchem.com/synthesis-of-succinic-anhydride/

Synthesis of Acetic Formic Anhydride http://www.prepchem.com/synthesis-acetic-formic-anhydride/

Thursday, August 29, 2019

I worked a very long day yesterday but I managed to get that block of sodium metal I've had for ages all cleaned up. I watched NileRed's video on how to do it and it turned out to be very easy. I was a little worried since the block of sodium I had was covered in this peach colored substance but when I melted it in mineral oil I found that the surface layer of crud was much thinner that I had previously thought. Another point for eBay sellers of chemicals.  I wasn't able to fully clean it last night so I will finish it tonight. An added bonus was that I was able to break up that block of sodium into many little beads which is fantastic. I only need small amounts at a time. Once this sodium metal is fully cleaned I will keep it stored under dollar store mineral oil just like the lithium and potassium already are. And once the THF arrives I can make sure that open bottles of the stuff stay anhydrous by putting a small, clean bead of sodium into the bottle. This is all working out BEAUTIFULLY!!!

I have checked every single listing that I can find and I have confirmed that indole-3-acetaldehyde (a.k.a. tryptaldehyde) is not a listed chemical or a controlled substance. Nor is tryptamine which frankly stunned me. I think that a video on making tryptamine might be going a little too far but tryptaldehyde is totally fair game and should be edgy enough to get some subs and clicks without landing me in any kind of trouble.

Tryptamine is only one small step away from becoming dimethyltryptamine and I don't want people thinking that I am encouraging (or god forbid engaging in) that kind of thing. I am less worried about the anthranilic acid because for it to be misused you would have to 1) turn it into N-acetylanthranilic acid and 2) then you would have to react it with o-toluidine in order to form methaqualone. And if you were to search my lab one thing you would notice is the distinct lack of o-toluidine or anything that could be turned into to o-toluidine without undertaking a massive multi-step synthesis. Also, not all of that phthalic anhydride will be turned into anthranilic acid. I have a few other projects in mind for the rest of it after I am done with the anthranilic acid projects (the grape flavoring that doubles as an insect repellent, indigo dye, and the TLC research).

Actually I am very curious to see how well tryptaldehyde chelates metal ions for my TLC project. Anthranilic acid forms spectacularly stable complexes with transition metal cations and I want to see how I can expand on that. In anthranilic acid the metal is chelated to the ionized carboxyl group and the amino nitrogen lone pair according to some of the literature I've seen so far. However, I would think that given the structure of tryptaldehyde that it could form a coordinate covalent bond to metal cations via the amino nitrogen lone pair and the carbonyl lone pairs. I could be totally off on that one but the best way to find out is to do the experiment and see what you get. 

Wednesday, August 28, 2019

Reductive Amination with Sodium Triacetoxyborohydride - Modern Organic Synthesis in the Laboratory, pg 83

It was insanely expensive but I was able to find 120 mL of anhydrous THF for sale on eBay. I am going to clean that block of sodium I have so that I will have some sodium spheres to store it over when it arrives. I want that stuff to stay 100% dry. The stuff that I have is still very cloudy even after this second round over the sieves. I think that these aren't the best sieves in the world (or it's REALLY wet) but I am to the point where I am ready to try a different drying agent like magnesium sulfate. Can't find any info about attempting that very thing so will probably try it on a small scale. If it clumps then it's not just the sieves. Eventually I will be able to get it dry. I am going to have to distill it at some point and that's always fun. Distilling ethers is NOT my idea of a fun time. One must be very, very careful and there is always a loss because I don't dare distill it dry even with the BHT and sieves keeping the peroxides to a minimum. But I should be able to recover 50 mL of dry THF from that at least and then that stuff is going to be saved and cared for as if it were liquid gold. Hell I don't take that kind of care with the chloroauric acid so MORE than liquid gold! LOL!

Tuesday, August 27, 2019

The rain precluded doing any distillation today so I don't know if my second 2,2-dimethoxypropane experiment worked or not. Since it doesn't look like it's going to clear up anytime soon I decided to scrap it and try again the next time I have a day off. That gives me time to dry the acetone and methanol more thoroughly anyways so that might be a good thing.

I've decided to scrap trying to do a synthesis of anthranilic acid from naphthalene. It looks like phthalic anhydride from naphthalene is kind of a pain in the ass and since you can just buy phthalic anhydride cheaply and easily (100 grams for about $20 counting shipping on eBay) I am just going to start with that instead. The plan would be to convert some of the phthalic anhydride to phthalamine and then oxidize that with bromate to anthranilic acid. That is a very attractive pathway because it produces metal-free anthranilic acid that I can use to synthesize pure anthranilic acid-metal cation complexes that I can then compare with the products of the 2-nitrobenzoic acid reduction using metals in acid. I have been looking at other beta and gamma amino acids which should also form very stable metal complexes which could be used for identification of metal cations in solution by TLC on silica gel like conventional organic compounds. I need to do some research and come up with an appropriate mobile phase so that I can start monitoring the progress of these chemical reactions using TLC. I have plenty of plates. Just need a good protocol.

The other experiment I have going on that I hope will turn out to be video-worthy is the tryptaldehyde synthesis from tryptophan. I found a VERY interesting paper discussing the reaction kinetics of tryptophan oxidation using hexacyanoferrate(III) and catalyzing the reaction with Cu2+ ions. It looked very promising but while detecting the aldehyde and proving the reaction worked will be childs play (use of Brady's Reagent will produce a dinitrophenylhydrazone whose mp can be easily measured) I don't know how practical it is going to be trying to extract and purify the aldehyde from the reaction solution. Hopefully simple extraction with an organic solvent followed by evaporation under vacuum is all that will be required.

Videos that are DEFINITELY coming in the near-ish future are:
1) synthesis and isolation of acetone oxime using hydroxylamine
2) synthesis of isopropylamine by reduction of acetone oxime using sodium borohydride in refluxing methanol
3) synthesis and crystallization of sodium nitroprusside
4) synthesis and isolation of sodium hexanitritocobaltate(III)
5) Cleaning metallic sodium

Videos for the the coming months are:
1) attempt at diiodomethane (DIM) from dichloromethane by Finkelstein Reaction (general method for producing alkyl iodides)
2) synthesis of 1,2-diiodoethane (DIE) from ethylene glycol using phosphorus triiodide
3) Kagans Reagent by direct reaction of samarium metal powder with DIM and/or DIE in dry THF
4) Reduction of an organic compound using Kagans Reagent
5) Diethylamine from DEET
6) synthesis of an anthranilate based insect repellent / artificial flavoring (it's both!)
7) synthesis of disulfur dichloride
8) synthesis of thionyl chloride (and possibly phosphoryl chloride)
9) synthesis of indigo dye from anthranilic acid and chloroacetic acid

"Alternatively, the methanol can be dried from magnesium methoxide. Magnesium turnings (5 g) and iodine (0.5 g) are refluxed in a small (50-100 mL) quantity of dry methanol (from a previous batch) until all of the magnesium has reacted. The mixture is diluted (up to 1 L) with reagent grade methanol, refluxed for 2-3 hours then distilled under nitrogen." https://chem.libretexts.org/Ancillary_Materials/Demos%2C_Techniques%2C_and_Experiments/General_Lab_Techniques/Drying_Solvents

"Several years after Kagan’s seminal work, Imamoto described a more atom economical method for the synthesis of SmI2 using samarium metal and iodine as the oxidant in refluxing THF [at 65 C]. " Preparation of Samarium(II) Iodide: Quantitative Evaluation of the Effect of Water, Oxygen, and Peroxide Content, Preparative Methods, and the Activation of Samarium Metal, Michal Szostak, Malcolm Spain, and David J. Procter, Journal of Organic Chemistry (2012) 😳😍🥰 If I didn't need to use up any of my phosphorus producing 1,2-diiodoethane that would free up more for doing other cool experiments. It would also make producing this reagent FAR easier for the everyday person who might wish to make use of it. Think of it: a very powerful and versatile reducing agent able to compete with most hydride reducing agents made using nothing more than samarium metal powder, iodine, and anhydrous tetrahydrofuran. The THF is actually the harder one to find. The Chinese will happily sell you all the samarium metal powder and iodine you want for very reasonable prices. And while iodine is regulated and you shouldn't buy more than a couple hundred grams a year at most it is happily highly recyclable. 

Monday, August 26, 2019

After successfully producing an anthranilic acid-tin(II) complex I decided to look for a more effective way to produce anthranilic acid than by the use of 2-nitrobenzoic acid. Unless a synthesis pathway presents itself that does not use metals that idea is pretty much done for now although I will continue to run the odd experiment to see if I can eventually crack this problem just for fun. I think instead that I am going to buy 100 grams of phthalic anhydride, convert that into phthalamine and then open that ring up to produce anthranilic acid that way. What's also great about this is that I can open some phthalic anhydride up to produce phthalic acid and then compare that with the product that I get from the naphthalene oxidation with cold, alkaline KMnO4. I can't do that until payday though so until then I am going to continue working on the 2,2-dimethoxypropane synthesis. 

Melting point of Lithium = 180.52 oC, Sodium = 97.79 oC, Potassium = 63.5 oC, Rubidium = 39.3 oC, Cesium = 28.44 oC. I got the alkali metals out to play with finally. I think that I will do a video on cleaning up my sodium metal tomorrow. Perhaps I will see if I can melt that lithium into a single chunk as well. That could be pretty cool. Then I can use that sodium metal to keep the THF dry and I can use it to FINALLY keep some diethyl ether! Not only will it keep it 100% dry it will also keep peroxides from forming. That's a pretty nice two-fur if I do say so myself. :-) 

Friday, August 23, 2019

OK so I think I've got a much more efficient way of synthesizing isopropylamine. The plan now is to react acetone with hydroxyamine to form acetone oxime. This can then be reduced to isopropylaime by refluxing the oxime with sodium borohydride in methanol. That should do the trick. I have a protocol from PrepChem on synthesizing and isolating acetone oxime. Doing the reduction will be simplicity itself. And this may lead to a general way to produce primary and secondary amines that is much better than the ways I have previously considered.

I didn't get a chance to try the DEET experiment yesterday. I spent most of the day making bromine and fresh anhydrous magnesium sulfate as well as drying the living hell out of my molecular sieves. I wish I could come across a good method for synthesizing THF or find a good supplier for it. It's so damn hard to come by and I really need it for these lanthanide diiodide experiments. THF stabilizes the divalent lanthanide complex. However, it looks like isopropylamine will also work for that. Isn't it nice when things just kind of segway together into one overarching project? Makes things so much more convenient.

Thursday, August 22, 2019


Taken from "Reduction of Ortho-Nitro-Benzoic Acid to Anthranilic Acid"


Video Ideas

1. Acetone Oxime 
     1A Reduction of Acetone Oxime to Isopropylamine (diborane by borohydride with iodine?) INVESTIGATE FURTHER
2. Leuckart Reaction with Acetone to produce Isopropylamine NOT DO-ABLE
3. 2,2-dimethoxypropane (test first) INVESTIGATE FURTHER
4. Oxidation of tryptophan with hypochlorite VERY LOW YIELD
5. Kagan's Reagent INVESTIGATE FURTHER
     5A Samarium(II) iodide in anhydrous THF by reaction of samarium metal powder with either DIM or 1,2-DIE INVESTIGATE FURTHER

"Proof of Concept" Experiments

1. Finkelstein Reaction with DCM --> DIM REPEAT
2. Microscale synthesis of PI3 INVESTIGATE FURTHER
3. Microscale synthesis of 1,2-DIE INVESTIGATE FURTHER
4. 2-nitrobenzoic acid reduction --> anthranilic acid transition metal cation complex DONE
5. Sulfur trioxide synthesis INVESTIGATE FURTHER
6. Thionyl chloride synthesis DEPENDS ON THE PRACTICALITY OF PRODUCING SO3 (Can it be done as reliably as making Cl2?)

Tasks to Complete

1. Distill ethylene glycol
2. Make new batch of anhydrous magnesium sulfate for solvent drying. DONE
3. Dry THF
4. Make more bromine. DONE
5. Make dioxane

Wednesday, August 21, 2019

The more I look at it the more I think that I have cracked the TLC enigma. Complexing the cations with beta and gamma amino acids will result in pentagonal and hexagonal complexes between the metal cations and two amino acid substituents. With a beta amino acid like anthranilic acid these complexes are high stable and (I think) soluble in organic solvents. Since the organometallic complex should behave more or less like an organic chemical species it should be separable using conventional silica gel TLC. Detection would probably be via fluorescence although if an amino acid can be found that will complex with metal cations and then undergo another reaction where it acquires a strong color then that could make the task even easier. I may have to synthesize some designer beta and gamma amino acids in order to investigate this properly but I am pretty damn sure this will work.

Tuesday, August 13th, 2019

A thesis on the reduction of 2-nitrobenzoic acid to anthranilic acid. That paper also gives the synthesis of indigo blue from anthranilic acid. So I can make a new, cutting edge insect repellent AND indigo dye. OK I know what project I am working on now. I have just enough 2-nitrobenzoic acid to do both experiments. Since 2-nitrobenzoic acid is kind of a hard chemical to come across (unless you're ready to either make it or spend beaucoup bucks buying it) I want to make sure I get it right since I won't be able to replace it. That doesn't give me a lot to work with so far as getting all the bugs out of the reactions before filming them. But I think that it is do-able. https://archive.org/details/reductionofortho00pfaf/page/n15

As far as the DEET to DEA (diethylamine) project is concerned it is now just a matter of doing a run that actually works. If we can recover any DEA at all this time around I will be satisfied. We are having a heat wave today so I need to wait until my roomie comes home in a few hours with some ice before doing the experiment. But so long as we don't get any pop-up storms I will be able to give it another go this afternoon while I am working out the kinks to the 2-nitrobenzoic acid reduction. I was also thinking of playing with some metal chem today (because I feel like I've wasted the day if I don't) so maybe a nice anhydrous thulium salt or something could be cool. 

2-Nitrobenzoic Acid: off white powder, CAS Number = 552-16-9, molar mass = 167.12 grams/mole, melting point = 147.5 oC, boiling point = 340.7 °C at 760 mmHg, pKa = 2.47. Soluble in ethanol, ethyl ether, acetone, methanol, somewhat soluble in water (7.85 grams/liter), and chloroform, very slightly soluble in benzene and carbon disulfide. If heated to decomposition it emits very toxic fumes. 

Anthranilic Acid: odorless white or yellow solid, CAS Number = 118-92-3, molar mass = 137.138 grams/mole, melting point = 146 - 148 oC, boiling point = 200 oC (sublimes), pKa = 2.17 (carboxyl) and 4.85 (amino). Very soluble in chloroform, pyridine, soluble in ethanol, diethyl ether, slightly soluble in trifluoroacetic acid, benzene

Friday, August 9th, 2019

As it turns out samarium dihaldes are extremely sensitive to exposure to air. I realized this after attempting to repeat the previously wildly successful synthesis of samarium(II) bromide. I tried making the diiodide and dibromide of samarium and while I had some success with the dibromide (it began to break down rapidly on being exposed to air even while still in a red hot crucible) but with the diiodide I got absolutely nothing so far as I can tell. Only this slightly off-whitish yellow compound that does not dissolve readily in water. BTFOM what is is. (8/11/19: samarium oxyiodide or samarium oxide most likely) I desperately need to find descriptions of the samarium oxyhalides and their properties in the literature. 

Wednesday, August 7th, 2019

"Tennessee Eastman Acetic Anhydride Process
Acetic anhydride is produced by carbonylation of methyl acetate (methyl ethanoate) in a process that is similar to the Monsanto acetic acid synthesis. Methyl acetate is used in place of methanol as a source of methyl iodide. In this process lithium iodide converts methyl acetate to lithium acetate and methyl iodide, which in turn affords, through carbonylation, acetyl iodide. Acetyl iodide reacts with acetate salts or acetic acid to give the anhydride. Rhodium iodides and lithium salts are employed as catalysts. Because acetic anhydride hydrolyzes, the conversion is conducted under anhydrous conditions in contrast to the Monsanto acetic acid synthesis.
CH3CO2CH3 + CO → (CH3CO)2O " - https://en.wikipedia.org/wiki/Monsanto_process#Tennessee_Eastman_acetic_anhydride_process

Tuesday, August 6th, 2019

"Tryptaphan is oxidized by sodium hypochlorite, resulting in the aldehyde (this special reaction of alpha amino acids was well studied in the '30s, one ref here: http://chemistry.mdma.ch/hiveboard/rhodium/pdf/tryptophan.st... )" - http://www.sciencemadness.org/talk/viewthread.php?tid=39224

"Reaction between NaOH and DEET in a solution of water and ethanol (say, 50/50 mixture) should proceed relatively easily at room temperature. I'd recommend magnetic stirring if possible, and having a heating option available in case the reaction decides to proceed slowly. A sign that the reaction is proceeding would be heat. I doubt the reaction would take more than an hour or so once started. Distillation should be simple enough. Diethylamine boils at 56C, ethanol at 78C, water at 100C, and DEET at 111C. Separation of fractions shouldn't require any special distillation equipment unless your heating mantle unfortunately happens to be a brick of thermite. And yes, I would recommend collecting only the fraction that comes over at around 56C." - http://www.sciencemadness.org/talk/viewthread.php?tid=954

OTC Hydrolysis of N,N-diethyl-meta-toluamide (DEET) to Diethylamine and M-toluic acid

"To a 250ml autoclavable media bottle is added in order, 175ml N,N-diethyl-meta-toluamide (98.11% comerc grade, $15) followed by 40ml 70% EtOH. the media bottle is capped and vigorously shaken for one minute. the EtOH and DEET should now be a homogenous mixture. to this solution is added 40g NaOH and once again capped. the media bottle containing the mix is now sealed and heated in a hot water bath (crock pot set on low) added to the bath at 55*C (125*F) ending at 70*C (160*F) periodically agitating for the length of time it takes to completely dissolve the NaOH plus 1.5hr. the solution should now be a deep yellow color the crock pot is turned off and allowed to cool to RT. it is removed from the bath and allowed to stand at RT for one day minimum. the bottle will then be carefully opened after cooling in the refrigerator for 1hr. observed was the strong smell of diethylamine, no longer did it smell of DEET and EtOH. the solution is fractionally distilled (don't forget boiling chips, this stuff likes to bump) collecting the fraction along a 9 degree temperature arc centered on 55*C (51-59*C). the solution may solidify towards the end of the distillation and a small amount of DH2O can be added to liquify the waxy mass of M-toluic acid and NaOH. total yield form approximately 225 ml of solution was 57ml of crystal clear diethylamine in freebase form. 25.3%.
MeOH can be used in a pinch but i like EtOH, it mixes better with the DEET and has just enough water for the hydrolysis but not enough to cause separation. Diethylamine C4H11N 73.14g/mol boiling point 55.5*C (131.9*F). N,N-Diethyl-M-Toluamide C12H17NO 191.27g/mol boiling point 288-292*C (550.4-557.6*F). M-toluic acid C8H8O2 136.15g/mol boiling point 263*C (505.4*F) (melt at 111-113*F). Ethanol C2H6O 46.07g/mol boiling point 78.4*C (173.12*F). Methanol CH4O 32.04g/mol boiling point 64.7*C (148.4*F). Water H2O 18.015g/mol boiling point 100*C (212*F)." - http://www.sciencemadness.org/talk/viewthread.php?tid=24131 (Spelling Errors Fixed)

Monday, July 29th, 2019

I keep putting off the GeI4 experiment because I keep thinking of things that need to be checked. However, no matter how I look at it I can't see a reason why it wouldn't work. My idea is to create germanium tetraiodide in exactly the same way I would create tin tetraiodide except for the GeI4 dichloromethane is replaced with chloroform. I2 will still dissolve readily in chloroform and if germanium metal is refluxed in that solution it should theoretically produce GeI4 which is also soluble in chloroform. That will remove any passivating crust of GeI4 from the metal as it forms which should keep the reaction going. Again, almost exactly the way tin tetraiodide is made. It should work. I think. DCM might also work for GeI4. Not sure because the lit doesn't say anything about that one way or the other. It just references chloroform and a few other non-polar solvents that I don't have.

I had no idea that trichloroacetonitrile could be of such utility in organic synthesis! I only looked it up because I was thinking about chloral earlier and was curious about other chlorinated analogs of common compounds. This is one of those things where I would never have looked at this but for idle curiosity and my curiosity was rewarded beyond anything I could have imagined. "...the chlorination of acetonitrile saturated with hydrogen chloride leads to pure trichloroacetonitrile even at 50-80 °C in good yields. Due to the high reactivity of the chlorine atoms, trichloroacetonitrile can be used (especially in combination with triphenylphosphine) to convert allylic alcohols into the corresponding allylic chlorides. With carboxylic acids, acyl chlorides are obtained." Could this be a viable general synthetic pathway to acyl chlorides? The mind boggles at the possibilities! And that's not all trichloroacetonitrile is good for! Check out the Wikipedia article for a larger listing: https://en.wikipedia.org/wiki/Trichloroacetonitrile#Use

Sunday, July 28th, 2019

Cl2 + I2 --> 2ICl
2ICl + 2H2O --> 2HCl + 2HI + O2

The HCl and HI can be separated by fractional distillation. Azeotropic HCl boils at 110 oC while azeotropic HI boils at 127 oC. This should be a viable pathway to generate hydriodic acid from elemental iodine. 

Thursday, July 25th, 2019

The more research I do the more the "Breeder Reactor in a Bottle" experiment looks feasible. There is one minor problem in that Radium226 may not be radioactive enough for measurable results to be obtained. The more I look at it the more I think that Americium241 AND Radium226 would be the way to go. Both emit alpha particles with energies in the 4+ MeV range with Americium241 emitting an alpha particle with 5.48 MeV of energy. This is in the same neighborhood as alpha particles given off by Plutonium238 and Polonium210 which are the usual alpha sources used to induce Beryllium9 neutron emission. It should be more than adequate to react with Beryllium9 to produce excited Carbon13 which will then decay to ground state Carbon12 with emission of a fast neutron. This can be moderated by heavy water or plain old graphite powder to produce thermal neutrons which should be able to bind to Thorium232 or Uranium238 to produce Uranium233 or Plutonium239, respectively.

Unfortunately I don't have a gamma ray spectrometer so I wouldn't be able to detect those isotopes directly but since U233 and Pu239 have much shorter half lives than Th232 or U238 a general increase in radioactivity should signal a successful experiment. The actual reactor bottle would have to be very small, perhaps 10-20 mL in volume at the most (20 is probably way too big for the very tiny amounts of reactants I would be using). As far as shielding from the neutron radiation (the biggest concern by far) I have already come up with a way to totally mitigate that. Store the reaction bottle inside another bottle full of a concentrated solution of a soluble boron compound and a soluble cadmium compound. Boron and cadmium are efficient neutron absorbers as is the water they would be dissolved in. In the event of an accident the reaction bottle can simply be broken inside the shielding bottle. The solution in reaction bottle would mix with the solution in the shielding bottle which would both dilute it to harmlessness AND shut down all nuclear reactions pretty much completely. So it should be extremely safe. I suppose that lead shielding could be used around the shielding bottle but it won't be necessary. Lead is not always the wisest way to go anyways. Bremsstrahlung is a thing.

Another issue is that I have not been able to confirm whether this is strictly legal or not. Everyone just assumes it would be a problem. But these are the same people who assume you can't buy thorium, uranium, radium or americium without 40 different permits which is just plain false so their opinions don't carry a lot of weight. 12 year olds can build fusion reactors in their garage and people call them brilliant. Why can't I put together 5 mL of a breeder reactor solution? A breeding reactor solution has never been done to my knowledge. It absolutely should work. It probably just isn't the most efficient way to go about producing fissionable material which is why it's not used by the military or the nuclear industry.

If natural uranium were used instead of depleted uranium then it is conceivable that some of the neutrons would be consumed causing U235 to fission. This is undesirable as without a gamma ray spectrometer there is no way to distinguish between an increase in radioactivity caused by fission of U235 (and its decay products) and that caused by decay of freshly minted U233/Pu239. While the amount of U235 is very small (~0.7%) I don't know if it would be detectable or not. Probably would be best to use depleted uranium in the experiment just to be sure.

Saturday, July 27th, 2019

If you combine trichloroisocyanuric acid with azeotropic hydrobromic acid will that give you bromine monochloride?

Monday, July 22, 2019

Radium226 → Radon222 + α(4.871 MeV). Ra226 half life = 1600 years. Note: Subsequent γ emission of Rn222 at 186 keV is possible. 

Americium241 → Neptunium237 + α(5.48 MeV) + γ(59.9409 keV). Am241 half life = 433 years.

Beryllium9 + α(4.871 MeV) or α(5.48 MeV) → Carbon13(Excited) → Carbon12(Ground) + n 

Sources: Wikipedia (Isotopes of Radium, Beryllium9, Americium241), Science Direct 

Possible laboratory scale synthesis of phosgene? ZrO2 + 2 CCl4 → ZrCl4 + 2 COCl2

Sunday, July 1th, 2019

What would happen if you created a solution of radium 222, americium 241, beryllium 9, and thorium 232 (or uranium 238) salts in heavy water? Would you have created a mini breeder reactor in a scintillation vial if everything was concentrated enough? It would be easy to detect. All you would have to do is create the solution and then watch for an increase in radioactivity. You would need the radium and americium because they give off alpha particles with enough energy to induce the beryllium to emit neutrons which would then be moderated by the heavy water and would bind to some of the thorium or uranium atoms creating uranium 233 or plutonium 239, respectively. I wonder if it would work better in light water with graphite particles suspended in the solution by stirring, increased viscosity from a high concentration of the salts, or both? A nuclear reactor in a bottle... :-D

Friday, July 12th, 2019

The new reagent library is proving to be very useful. Already I've been able to use it to figure out exactly what the tantalate solution that I made yesterday is doing. Well, not exactly but close. It definitely contains dissolved potassium tantalate since it makes a light ppt with magnesium sulfate and strontium chloride and a very voluminous ppt with barium acetate. However it did not throw down a ppt with silver nitrate which it should have done. I am not sure if the pH is the problem. I have yet to acidify it or boil it. But I am about to play with this some more. We have a storm about to come through but that shouldn't stop me from filming a synthesis of tantalum pentoxide from the metal. I thought about putting niobium in this one too since it's chemistry is VERY similar to tantalum but I might have a different use for the niobium I have so I am going to hold off on that for now. The next elements I will tackle after tantalum will be zirconium and hafnium and then I will probably do some stuff with antimony. My experiments with samarium continue. Samarium(III) iodide hexahydrate has definitely been produced and it's as free of the oxyiodide as I can possibly make it. The next step with that would be to grind it up with 10x it's mass of ammonium iodide and then heat it up. I wonder if I can do that in some kind of apparatus because I am going to lose a TON of iodine during that process and I try to recycle every bit of precious iodine that I can. If I could capture the vapor that would be really helpful. 

Wednesday, July 3rd, 2019

Antimony trioxide can be produced by fusing antimony with potassium nitrate and potassium bisulfate. Dissolving in concentrated nitric acid produces a mixture of oxides. Antimony pentoxide can be reduced to the trioxide by treatment with sulfur dioxide or hydriodic acid. Sulfur dioxide can also be formed by the action of dilute sulfuric acid on sodium sulfite or bisulfite. 

Dissolve tantalum by fusion with potassium hydroxide. Boil this tantalate with a dilute acid to produce tantalum pentoxide gel. 

"Hydrated tantalum pentoxide is a white, amorphous substance. A crystalline form is stated to be obtained when tantalum pentachloride is treated rapidly with water; the precipitate thrown down is dried slowly and again treated with water. A granular variety is produced when sodium tantalate solution is treated with sulphur dioxide and the flaky precipitate is dried. Tantalum pentoxide gel becomes incandescent and loses its water content when it is rapidly heated to 500° C., unless it has been previously aged by washing with water. This "glow " phenomenon is also displayed by hydrated chromium sesquioxide, by aluminium oxide, and by titanium dioxide. " www.atomistry.com

Wednesday, June 26th, 2019

Niobium can be dissolved in hydrofluoric acid. Tantalum burns when gently heated with chlorine. It reacts slowly with sulfur and selenium. It is slowly dissolved in boiling concentrated sulfuric acid. It is soluble in hydrofluoric acid. Fusion of niobium or tantalum with caustic potash in air yields niobates or tantalates, respectively. 

Iridium can be dissolved by using the same KOH and KNO3 mixture that I used to dissolve the ruthenium yesterday! I am so excited that I finally found a straightforward way to change metallic iridium into something chemically interesting! The reaction produces iridates (potassium iridate?)

Iridium can be converted to potassium chloroiridate by the action of chlorine on a hot mixture of iridium powder and potassium chloride. Precursor to thallium chloriridate (thallium nitrate and potassium chloriridate). Dissolving iridium black in hydrochloric acid produced iridium tetrachloride while any trichloride produced is converted to the tetrachloride with aqua regia. Lithium iridate possible synthesis: fusion of lithium and iridium powder in air? 

Monday, June 24th, 2019

Iridium can be converted to iridium disulfide by the action of an alkali polysulfide finely divided iridium. This can then be decomposed by fuming nitric acid or aqua regia (however what it decomposes into is not stated).  http://iridium.atomistry.com/iridium_disulphide.html

Rhodium dissolves when fused with potassium hydrogen sulfate. Iridium and platinum do not. http://rhodium.atomistry.com/chemical_properties.html

Sunday, June 23rd, 2019

I have become quite caught up in my latest idea of rendering as many elements as possible into solutions for easy use in future reactions and analyses. It makes sense to do it for as many elements as possible and to make these solutions out of simple compounds likely to be encountered or useful in future synthetic and analytical work. Chloroplatinic acid, perrhenic acid, and palladous chloride were just the beginning. I found out that ruthenium can be dissolved in a molten mixture of KOH and KNO3 and the resulting green solid dissolved in water to produce an orange solution of potassium ruthenate. It may also be possible to dissolve it in a mixture of hydrochloric acid and potassium chlorate (so hydrochloric and chloric acids) to produce perruthenate. That sounds dangerous. I cannot figure out if this powdered iridium I have will dissolve in aqua regia or not. Given what I have read I don't think that it will. However, I did find that iridium will react with sulfur at atmospheric pressure to form iridium disulfide and it may be possible to enter into iridium chemistry that way. I also found that iridium will dissolve in molten sodium cyanide and this may be the better method for rendering the iridium powder chemically reactive. 

Saturday, June 8th, 2019

Another day of rain. Yay. Rain dramatically limits what I am able to do; one of the prices one pays when one invests in things other than a fume hood. I still think that handling the various gasses/fuming liquids would be more trouble than it's worth. You would have to pipe it a fair distance away from the dogs and that would involve tens of feet of hosing that would amount to a LOT of surface area for volatile chemicals to condense on not the least of which is water vapor. While it would be possible to engineer the thing so it could drain that raises the question of how to handle the drainage from it. Moving the dangerous waste around is, funnily enough, a lot more damaging than just letting it dissipate into the environment as its generated. I've noted no ill effects whatsoever to the environment from my experiments as I have been conducting them. The only thing would be ozone damage from evaporation of the chlorinated solvents like dichloromethane which is unavoidable but which is kept to a minimum already for economic reasons. It's a bit of enlightened self-interest really. And if a fume hood isn't practical during the monsoon season that is winter around here then it sure as hell isn't practical in summer during which I have seen it go without raining at my house for more than 60 days at a time. 

Thursday, June 6th, 2019

Although everything is barely functional I've decided to go ahead and start recording my chemical adventures on my little blog here. I am thrilled to have my own personal website again after so many years of not having one. Long ago my ex-husband set up a server in our basement and I created my first website on there. At that time the sole purpose of my website was to make my school notes accessible to myself anywhere at anytime without having to carry around a backpack full of notebooks. It worked very well and after I lost a place to host the site during my divorce I decided that when the time was right I would create an even better website than my old one and pay for everything myself. Since the "poor" in Poor Mans Chemist isn't just a metaphor it took a few years before I was in a position where I could spend money on non-essential extras like this. But now that I have it I am going to use it as much as possible. My goal is to create a website that not only fulfills the function of making my notes available to me anywhere I have internet access but that also can act as a starting point for aspiring home chemists who are looking for reliable information on how to set up their own labs and properly use them. 


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