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All 12 posts Subject: PTC alternatives Please login to post Down

Antibody2
(Hive Addict)
04-16-03 16:46
No 427301
      PTC alternatives

curious if bees might be able to suggest alternatives to Aliquat 336 as a PTC. Antibody is specifically curious about the viability of polysorbate as a replacement in Barium's new C=C reduction variation.

opinions? alternatives?

Vitus_Verdegast
(Hive Bee)
04-16-03 20:11
No 427352
User Picture       maybe cetrimide can substitute?

Hxadecyltrimethylammonium bromide ("Cetrimide") is still quite lipophilic so maybe it can substitute for Aliquat 336. It is cheap and easy to get, as it is used in the preparation of shampoo's :

http://www.hkmj.org.hk/skin/govformu.htm

Don't know if a polysorbate will work, do you have any refs on the subject ?

What about PEG400?

http://www.ealasaid.com/fan/lorrelibrary/b-wing/bc/intro.wav

Antibody2
(Hive Addict)
04-16-03 22:06
No 427384
      interesting link, vitus.

interesting link, vitus. no i've no refs just a litre of polysorbate 20

just did a couple of tests and while the polysorbate 20 seems to disolve in either toluene or dcm, when water is added regardless of the amount of stirring the aqueous layer reforms above the dcm. With toluene addition of water causes this puss like suspension (it stays suspended). Never having worked with PTC's before its difficult to say whether it was truly successful or not.

its looks as though it may complicate work-up

Lilienthal
(Moderator)
04-16-03 22:37
No 427398
User Picture       Why should polysorbate act as a PTC for ...

Why should polysorbate act as a PTC for organic compounds?

Rhodium
(Chief Bee)
04-16-03 23:34
No 427415
      PEG 400 PTC

Polyethyleneglycols with molecular weights of 200-600 (particularly PEG 400) works very good as a PTC, and can usually be crashed out from the organic phase by dilution with ether...

In some reactions the free OH groups can also be modified to bear other substituents to modify its properties, for example by attaching phenylphosphines and adding Pd salts you can make a recoverable homogenous catalyst support for all kinds of Pd-catalyzed reactions, as a substitute for Pd(PPh₃)₃. Example: Post 446706 (Rhodium: "PEG as support/PTC in Pd-catalyzed cross-couplings", Chemistry Discourse)

moo
(Hive Bee)
04-17-03 00:34
No 427429
      Check out Post 290770 .

Check out Post 290770 (foxy2: "Right one", Chemicals & Equipment). Yes, it is quite ghetto but at least they tested several fabric softeners. Comfort worked quite well.

foxy2
(Distinctive Doe)
04-17-03 02:41
No 427465
User Picture       moo Since you seem to have the article, maybe...

moo
Since you seem to have the article, maybe you could post the details?
Or is this basically all there is?
Comfort worked quite well.

moo
(Hive Bee)
04-17-03 07:57
No 427515
      OTC fabric softener phase transfer catalysts
(Rated as: excellent)

Most of the article discusses educational aspects of the reaction so I'll type the parts that most benefit bees along with the test reaction so that it is clear how they tested it. It is basically the addition of dichlorocarbene, generated from NaOH and CHCl₃ under PTC conditions, to cyclohexene. This is the article that makes me grin whenever walking past the fabric softeners in the supermarket. smile

Fabric Softeners as Phase Transfer Catalysts in Organic Synthesis, J. Chem. Educ. 68, 69-70 (1991):

[...]

Experimental

[...]

To 10 mL of 50% (w/w) aqueous sodium hydroxide solution in a 100-mL round-bottom flask was added 5 mL of cyclohexene and 20 mL of chloroform. Then 2 mL of the fabric softener to be tested was added to the mixture. The stoppered two-phase mixture was stirred magnetically at ~1000 rpm using a 1-in. Teflon-coated stirring bar. The reaction mixture turned turbid as some white emulsion started to form after 15 to 20 min.

The reaction was monitored by GC at 15- to 20-min time intervals. The stirrer was turned off, and 1-mL GC samples were taken from the top organic layer of reaction mixture. The samples were passed through some anhydrous sodium sulfate packed in a Pasteur pipet to remove any of the white emulsion and moisture. The GC experiments were carried out using a 3 mm X 1 m SE-30 column installed in a Hitachi 163 gas chromatograph with flame ionization detector and a Hitachi 561 recorder. In a larger scale experiment, 15 mL of the sodium hydroxide solution, 20 mL of chloroform, 20 mL of cyclohexene, and 8 mL of the fabric softener were stirred for 5 h as above. after simple work up and distillation (collected between 192-198 °C), NMR pure 7,7-dichlorobicyclo[4.1.0]heptane was obtained in 51% Yield¹.

Results and Discussion

The reaction times of each fabric softener used were summarized in the table. For 2 mL of the fabric softeners used, the reactions were completed within 2 h with the exception of one brand (run 4, table). Two control experiments were also carried out. Without the fabric softener, the reaction did not proceed as indicated by GC. When a typical phase transfer catalyst, Aliquat 336 (methyltrioctylammonium chloride, 2 mol % to cyclohexene) was used in the reaction, the reaction was also completed in 2 h. This indicated that the effect of 2 mL of fabric softener was roughly equivalent to that of 2 mol % of a typical phase transfer catalyst.

One sample tried did not work well as a phase transfer catalyst (run 4, table). It may be due to the fact that another active ingredient such as noncationic softening agent was used in the formula. It is also worth noting that the concentrated formula (run 3) did not work better as a phase transfer agent than the regular formula (run 2).

Place of Reaction
   Fabric softener    Manufacture cents/mL time (h)
--------------------------------------------------------
1. Soft Great Japan 0.14 1.50
2. Comfort    UK    0.16 1.33
3. Concentrated Comfort UK    0.23 1.33
4. Bonnie Hubbard Canada    0.12 >4^a
5. Softlan    US    0.13 2.00
6. Park'n Hong Kong 0.11 1.00
--------------------------------------------------------
^aReaction was not completed after 4 h.

[...]

References

1. J. Chem. Educ. 55, 350 and 429 (1978)

Antibody2
(Hive Addict)
04-18-03 16:31
No 427854
      they use it straight out of the bottle, wow.

they use it straight out of the bottle, wow. thanx moo

psygn
(Stranger)
04-20-03 17:03
No 428209
      I am also v.interested in this, particularly...

I am also v.interested in this, particularly as to the possibility of whether BzEt3N would bee a suitable substitute for Aliquat 336 in Barium's 2-phase borohydride redn.? Can anyone offer any light on this?

Thanks!

Vitus_Verdegast
(Hive Bee)
04-20-03 19:39
No 428228
User Picture       might work

Aliquat 336, or methyltrioctylammonium chloride, is a very lipophilic PTC (more than 20 C atoms), BzEt₃N⁺ Cl^- is quite hydrophilic.

On the other hand, "Phase Transfer Catalysts, properties and applications" (Merck-Schuchardt) states that tetraalkylammonium borohydrides are soluble in organic solvents. So it might work.

http://www.ealasaid.com/fan/lorrelibrary/b-wing/bc/intro.wav

java
(Hive Bee)
04-20-03 23:21
No 428263
      RE: PTC

I've recently taken interest in the PTC chemistry. Not being very familiar with it and only guided by the readings available in March's 5th edition text i've taken the task to find a PTC catalyst that will remove a OH and convert to an alkane as well as reducing a carboxylic acid to an alcohol or alkane or aldehyde.

I have read of the OTC PTC, some being Fabric softeners and just the whole idea of doing chemistry in this way increases my interest.

So I guess the only dumb question is the one that doesn't get asked .................java

We're all in this world together,
http://www.chiapaslink.ukgateway.net/

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	All 12 posts		Subject: PTC alternatives		Please login to post		Down


		Antibody2 (Hive Addict) 04-16-03 16:46 No 427301				PTC alternatives
						curious if bees might be able to suggest alternatives to Aliquat 336 as a PTC. Antibody is specifically curious about the viability of polysorbate as a replacement in Barium's new C=C reduction variation. opinions? alternatives?



		Vitus_Verdegast (Hive Bee) 04-16-03 20:11 No 427352				maybe cetrimide can substitute?
						Hxadecyltrimethylammonium bromide ("Cetrimide") is still quite lipophilic so maybe it can substitute for Aliquat 336. It is cheap and easy to get, as it is used in the preparation of shampoo's : http://www.hkmj.org.hk/skin/govformu.htm Don't know if a polysorbate will work, do you have any refs on the subject ? What about PEG400? http://www.ealasaid.com/fan/lorrelibrary/b-wing/bc/intro.wav



		Antibody2 (Hive Addict) 04-16-03 22:06 No 427384				interesting link, vitus.
						interesting link, vitus. no i've no refs just a litre of polysorbate 20 just did a couple of tests and while the polysorbate 20 seems to disolve in either toluene or dcm, when water is added regardless of the amount of stirring the aqueous layer reforms above the dcm. With toluene addition of water causes this puss like suspension (it stays suspended). Never having worked with PTC's before its difficult to say whether it was truly successful or not. its looks as though it may complicate work-up



		Lilienthal (Moderator) 04-16-03 22:37 No 427398				Why should polysorbate act as a PTC for ...
						Why should polysorbate act as a PTC for organic compounds?



		Rhodium (Chief Bee) 04-16-03 23:34 No 427415				PEG 400 PTC
						Polyethyleneglycols with molecular weights of 200-600 (particularly PEG 400) works very good as a PTC, and can usually be crashed out from the organic phase by dilution with ether... In some reactions the free OH groups can also be modified to bear other substituents to modify its properties, for example by attaching phenylphosphines and adding Pd salts you can make a recoverable homogenous catalyst support for all kinds of Pd-catalyzed reactions, as a substitute for Pd(PPh₃)₃. Example: Post 446706 (Rhodium: "PEG as support/PTC in Pd-catalyzed cross-couplings", Chemistry Discourse)



		moo (Hive Bee) 04-17-03 00:34 No 427429				Check out Post 290770 .
						Check out Post 290770 (foxy2: "Right one", Chemicals & Equipment). Yes, it is quite ghetto but at least they tested several fabric softeners. Comfort worked quite well.



		foxy2 (Distinctive Doe) 04-17-03 02:41 No 427465				moo Since you seem to have the article, maybe...
						moo Since you seem to have the article, maybe you could post the details? Or is this basically all there is? Comfort worked quite well.



		moo (Hive Bee) 04-17-03 07:57 No 427515				OTC fabric softener phase transfer catalysts (Rated as: excellent)
						Most of the article discusses educational aspects of the reaction so I'll type the parts that most benefit bees along with the test reaction so that it is clear how they tested it. It is basically the addition of dichlorocarbene, generated from NaOH and CHCl₃ under PTC conditions, to cyclohexene. This is the article that makes me grin whenever walking past the fabric softeners in the supermarket. Fabric Softeners as Phase Transfer Catalysts in Organic Synthesis, J. Chem. Educ. 68, 69-70 (1991): [...] Experimental [...] To 10 mL of 50% (w/w) aqueous sodium hydroxide solution in a 100-mL round-bottom flask was added 5 mL of cyclohexene and 20 mL of chloroform. Then 2 mL of the fabric softener to be tested was added to the mixture. The stoppered two-phase mixture was stirred magnetically at ~1000 rpm using a 1-in. Teflon-coated stirring bar. The reaction mixture turned turbid as some white emulsion started to form after 15 to 20 min. The reaction was monitored by GC at 15- to 20-min time intervals. The stirrer was turned off, and 1-mL GC samples were taken from the top organic layer of reaction mixture. The samples were passed through some anhydrous sodium sulfate packed in a Pasteur pipet to remove any of the white emulsion and moisture. The GC experiments were carried out using a 3 mm X 1 m SE-30 column installed in a Hitachi 163 gas chromatograph with flame ionization detector and a Hitachi 561 recorder. In a larger scale experiment, 15 mL of the sodium hydroxide solution, 20 mL of chloroform, 20 mL of cyclohexene, and 8 mL of the fabric softener were stirred for 5 h as above. after simple work up and distillation (collected between 192-198 °C), NMR pure 7,7-dichlorobicyclo[4.1.0]heptane was obtained in 51% Yield¹. Results and Discussion The reaction times of each fabric softener used were summarized in the table. For 2 mL of the fabric softeners used, the reactions were completed within 2 h with the exception of one brand (run 4, table). Two control experiments were also carried out. Without the fabric softener, the reaction did not proceed as indicated by GC. When a typical phase transfer catalyst, Aliquat 336 (methyltrioctylammonium chloride, 2 mol % to cyclohexene) was used in the reaction, the reaction was also completed in 2 h. This indicated that the effect of 2 mL of fabric softener was roughly equivalent to that of 2 mol % of a typical phase transfer catalyst. One sample tried did not work well as a phase transfer catalyst (run 4, table). It may be due to the fact that another active ingredient such as noncationic softening agent was used in the formula. It is also worth noting that the concentrated formula (run 3) did not work better as a phase transfer agent than the regular formula (run 2). Place of Reaction Fabric softener Manufacture cents/mL time (h) -------------------------------------------------------- 1. Soft Great Japan 0.14 1.50 2. Comfort UK 0.16 1.33 3. Concentrated Comfort UK 0.23 1.33 4. Bonnie Hubbard Canada 0.12 >4^a 5. Softlan US 0.13 2.00 6. Park'n Hong Kong 0.11 1.00 -------------------------------------------------------- ^aReaction was not completed after 4 h. [...] References 1. J. Chem. Educ. 55, 350 and 429 (1978)



		Antibody2 (Hive Addict) 04-18-03 16:31 No 427854				they use it straight out of the bottle, wow.
						they use it straight out of the bottle, wow. thanx moo



		psygn (Stranger) 04-20-03 17:03 No 428209				I am also v.interested in this, particularly...
						I am also v.interested in this, particularly as to the possibility of whether BzEt3N would bee a suitable substitute for Aliquat 336 in Barium's 2-phase borohydride redn.? Can anyone offer any light on this? Thanks!



		Vitus_Verdegast (Hive Bee) 04-20-03 19:39 No 428228				might work
						Aliquat 336, or methyltrioctylammonium chloride, is a very lipophilic PTC (more than 20 C atoms), BzEt₃N⁺ Cl^- is quite hydrophilic. On the other hand, "Phase Transfer Catalysts, properties and applications" (Merck-Schuchardt) states that tetraalkylammonium borohydrides are soluble in organic solvents. So it might work. http://www.ealasaid.com/fan/lorrelibrary/b-wing/bc/intro.wav



		java (Hive Bee) 04-20-03 23:21 No 428263				RE: PTC
						I've recently taken interest in the PTC chemistry. Not being very familiar with it and only guided by the readings available in March's 5th edition text i've taken the task to find a PTC catalyst that will remove a OH and convert to an alkane as well as reducing a carboxylic acid to an alcohol or alkane or aldehyde. I have read of the OTC PTC, some being Fabric softeners and just the whole idea of doing chemistry in this way increases my interest. So I guess the only dumb question is the one that doesn't get asked .................java We're all in this world together, http://www.chiapaslink.ukgateway.net/

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