DE279012C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

The china alkaloids produce hydrogen with a moderate oxidation with loss of 2 atoms Ketones (cf. Rabe, Ber.4o [1907], p. 3655; Ann. 364 [1909], p. 330).

It has now been found that such quinaketones under the action of organic

N
I.

i.

CH ₈ O-

CH ₃ -MgJ = CH, O-magnesium compounds and the subsequent treatment with water convert into new alcohols. When treating quininone,. the ketone from quinine with methyl magnesium iodide, the reaction proceeds z. B. in the sense of the following formulas: 40

I.
CO-R

2.

CH ₃ O-

+ H ₂ O = MgOHJ + CH ₃ O-

C (OMgJ) _{1 row}

CH, C (O ¹ H) -CH ₃ R

55

(in the above formulas, R denotes the quinuclidine residue).

According to their formation, the new compounds belong to the tertiary alcohols ; they differ from the china alkaloids with a secondary hydroxyl in that they contain more than one alkyl. These C homologues of the quinaalkaloids are remarkable in physiological terms valuable properties, especially pronounced action against trypanosomes; they should be in the. Therapy use.

Example I.
C-Met hy! Cinchonin.

To a solution of methyl magnesium iodide, prepared from 2.5 parts of magnesium, 15 parts Iodomethyl and 50 parts of absolute ether, a solution is added dropwise with shaking of 7.5 parts of cinchoninone in 150 parts of ether. , This produces a sulfur-yellow precipitate.

After standing for a while, first hydrous ether, then chlorammonium solution is added and the essential solution quickly lifted off. C-methylcinchonine soon separates from it away. Further quantities are obtained

.15 when concentrating the mother liquor.

C-methylcinchonine crystallizes from aqueous ether or from dilute ether Alcohol in white shiny needles. They contain 2 molecules of crystal water that melt at 116 to 117 ° and are easily soluble in alcohol, sparingly soluble in ether, insoluble in Water.

For: C ₂₀ H ₂₄ ON ₂

calculated: found:

C = 77.92 percent, = 77.75 percent,
H = 7.80 - = 7.84

The monochlorohydrate crystallizes from water as a colorless crystalline powder with a melting point of 270 °. 30th

Example II.

C-methylquinine.

Its representation is based on 2 parts of magnesium and 15.5 parts of iodomethyl and ether on the one hand, 7 parts quininone and benzene on the other. After implementation the reaction product is mixed with aqueous ether and then with chlorammonium solution treated. From the lifted ethereal solution one obtains, especially on the addition of Water, the formed C-methylquinine. Further amounts crystallize after concentration. The C-methylquinine crystallizes from dilute alcohol in colorless needles, which Contain 2 molecules of crystal water and melt at 115 °.

For: C ₂₁ H ₂₆ O ₂ N ₂

calculated:

C = 74.55 percent,
H = 7.69

found:
= 74.37 percent,
= 7.75 - ■

The monochlorohydrate is very easily soluble in water and melts at 252 °.

Example III.
C-phenyldihydro quinine.

A solution becomes an ethereal solution of 5 molecules of phenylmagnesium bromide given by ι molecule dihydroquininone (Irschick, dissertation, Jena 1913) in benzene. When the reaction is complete, moist ether and then chlorine magnesium solution are added. After adding water, water vapor is blown through the lifted ethereal solution until the as Diphenyl formed by-product is removed. The leftover oil becomes with ether shaken out and mixed with a little alcohol; it gradually separates C-phenyldihydroquinine away. The colorless crystals obtained in this way contain 1 molecule of crystal alcohol; they melt at 181 to 182 °.

C ₂ H ₅

For: C ₂₈ H ₃₀ O ₂ N ₂ , calculated·: C ₂ H ₅ OH = 75.00 percent, found: C. = 8.04 -. = 75> ° 7 percent, H = 10.27 = 8.05 OH = 10.28

Claims (1)

Patent claim: Process for the preparation of homologues of the china alkaloids, characterized in that, that one quinaketone in the usual way with the help of organic Magnesium compounds converted into tertiary alcohols.