(Master Searcher)
03-25-02 16:05
No 287823
      JA44-10776 (MDP2P from dichloroisosafrole)
(Rated as: excellent)

In reference to Post 287795 (not existing)

Here's some details on Japanese patent 44-10776 which were read by a Japanese speaking non-chemist to a non-Japanese speaking chemist. 

Note:  The chemical words are written in Katakana (a Japanese alphabet).

In column 1 it discusses making phenylacetone derivatives from phenyl-dihalopropane derivatives and R1 and R2 being either hydroxy, alkoxy or methylenedioxy groups.  In column 2, it looks like it discusses prior art references and also says something about blood pressure.  Lower down column 2 it discusses making the dihalo derivative, but doesn't give details.  It sounds like the dihalo derivatives are made from phenylpropene derivatives.   The translation of examples 1 and 2 are shown below.  BTW, two words in the examples sound a lot like kalium and natrium (potassium and sodium) which might have been borrowed from German, which seems interesting.  I think those words are also the Latin names (or similar) for the elements.  I looked at a Japanese chemical journal before and found both Japanese and German articles in it.

Update:  a Japanese translator told me that a lot of Japanese chemical words were borrowed from German, typically old ones, but some come from English.


Method of making phenylacetone derivatives

Example 1

75 g. of 15% potassium hydroxide is added to 23.3 g. 1-(3,4-methylenedioxyphenyl)-1,2-dichloropropane and agitated 10 hours, cooled to room temperature, extracted twice with 200 ml benzin (benzene or benzine?), dried and evaporated (with heat) to get 15.2 g. 3,4-methylenedioxyphenylacetone (yield 85.4 %).  The boiling point is 149-151 C/10mm Hg.

Example 2

80 g. 20 % sodium hydroxide is added to 33.8 g. 1-(3,4-dimethoxyphenyl)-1,2-dibromopropane (melting point 90-93 C.) and boiled for 12 hours.  After steam distillation and extraction with benzin (benzene or benzine?) 18.4 g. of a light yellow color oil is obtained.  It is pure 3,4-dimethoxyphenylacetone (yield 95.0 %).  The boiling point is 133-137 C/10mm Hg.


ad terra incognita per ars artis gratia
(Master Searcher)
03-25-02 16:26
No 287830
      Katakana  Bookmark   

This is a good start for learning Katakana.  The top row are vowels. Below those are corresponding consonants.  Voiceless compound sounds are to the right and voiced compound sounds are at the bottom.

ad terra incognita per ars artis gratia
03-26-02 04:07
No 288072
      benzin  Bookmark   

Benzin is a german word and means petroleum ether, boiling point about 100-140 degree centigrade.
(Master Whacker)
03-27-02 21:46
No 288855
      solvent choice  Bookmark   

I reported several times over the years that this reaction using dibromodihydroisosafrole only produced tar.  I recently found my notes and discovered that an aq. soln of base was used.  This must have been the reason for failure.  I bet if ethanolic hydroxide is used it will work as stated in Sam's translations.  Perhaps an addendum should be added to that post explaining that aq. solvents must not be used.
(Chief Bee)
03-27-02 22:20
No 288866
      Dibromoisosafrole not used in patent  Bookmark   

Ritter: The patent says to use the 3,4-dimethoxyphenyl-1,2-dibromopropane for 3,4-MeO-P2P and
3,4-methylenedioxyphenyl-1,2-dichloropropane for MDP2P. 3,4-methylenedioxyphenyl-1,2-dibromopropane to make MDP2P is not mentioned. While I cannot figure out what the difference would be, the patent text is definitely not disproven as of yet.
07-06-02 12:17
No 329376
      bump  Bookmark   

Has any more work been done with this?
Old lady at the supermarket foaming at
mouth for more information.

over and under, then back to the start
this sidewalk's bottom is the same as its top
(Chief Bee)
07-06-02 12:43
No 329380
      No, but if you are interested in actually carry ...  Bookmark   

No, but if you are interested in actually carry out the procedure, I could sit down and make a small instruction manual for you, where I describe how I would have done it if I had the opportunity to do that.

Entropy just isn't what it used to be.
07-14-02 17:35
No 332569
      I found uemura's dibromo write-up on your page ...  Bookmark   

I found uemura's dibromo write-up on your page and was
curious if the same procedure of hydration applies to
the dichloro as well, or if it is even required, as
what information I can gather from the Japanese patent
and related discussion seem to discount hydration
as a harmless byproduct of water-contaminated solvents
which wouldn't alter its reaction with KOH.

I fiddled around with my calculator and came up with
some numbers, I was also wondering if these would be
correct for the dichloro version of this route:

1mol alkene          162.0g        x620 = 100.0g
1mol dichloro        233.0g        x620 = 144.5g
1mol dichlorhydrine  214.5g        x620 = 133.0g
1mol epoxide         178.0g        x620 = 110.36g
1mol KOH              56.1g        x620 = 34.78g
1mol HCl              36.4g        x620 = 22.54g

100g alkene + 44.5g Cl2 = 144.5g dichloro-alkene
144.5g dichloro-alkene + 10.5g H2O = 133.0g dichlorohydrine-alkene + 22.54g HCl
133.0g dichlorohydrine-alkene + 34.78g KOH = 110.36g alkene-epoxide + 46.19g KCl + 11.16g H2O

Theoretically, I think.

(Hive Bee)
07-14-02 20:20
No 332626
      isnt this procedure the same as "Yuki et al, ...  Bookmark   

isnt this procedure the same as "Yuki et al, Japanese Patent 69:10,776
        Chemical Abstracts 71, 30220e (1969) "

found on ../rhodium/chemistry /tcboe/chapter5.htm ?

A nut for a jar of tuna.
-The drive by palindromer
07-14-02 21:10
No 332649
      Ahh.. more details...  Bookmark   

Thank you for pointing that out, I guess I should search
more on rhodium's site and less on the hive :)

I see.. they used two molar equivalents of KOH for the reflux, uemura's writeup only uses a 1.16:1 ratio.

Is that for a reason or was Yuki just being cautious?
I wonder if the reaction time can also be reduced,
I bet TLC would be helpful here.

over and under, then back to the start
this sidewalk's bottom is the same as its top
(Chief Bee)
07-15-02 05:04
No 332805
      alchemy_bee: The Yuki reference is exactly what's ...  Bookmark   

alchemy_bee: The Yuki reference is exactly what's translated above in the post by PolytheneSam.