US2176181A - Method of manufacturing organic chlorine and bromine derivatives - Google Patents

Abstract

Organic chlorine or bromine compounds are produced by reacting chlorine or bromine with salts of organic carboxylic acids with metals, particularly with metals of the first, second, and third groups of the periodic system. Thus, simple acids yield alkyl halides; a -hydroxy acids yield hydrohalogen compounds of the aldehydes; hydroxy acids in which the hydroxyl is not in the a -position yield hydroxyalkyl halides; polyhydroxy acids with one hydroxyl in the a -position yield hydrohalogen compounds of hydroxy-aldehydes; a -halogen fatty acids yield 1,1-dihalogen hydrocarbons; dicarboxylic acids yield dihalogen hydrocarbons; ester acids yield halogen fatty acid esters; a -keto acids yield acid halides; cycloalkane mono- and polycarboxylic acids yield cycloalkyl halides; and amino acids (other than a -amino-acids) yield halogen alkylamines; in each case with the liberation of carbon dioxide. In examples, bromine is reacted with the silver salts of palmitic, lauric, acetic, coconut fatty acids, hydroxy-palmitic, a -brom-stearic, 9--10 dichlor octadecanic (from chlorinated oleic acid) sebacic, sebacic monoethyl ester, pyroracemic and mandelic acids, yielding pentadecyl, undecyl, methyl and mixed alkyl bromides, an aldehyde hydrobromide, dibromheptadecane, 1-brom-8,9-dichlor heptadecane, 1 - 8 - dibrom octane, 9-brom-nonylic acid ethyl ester, acetyl bromide, and benzaldehyde hydrobromide respectively; chlorine is reacted with silver stearate yielding heptadecyl chloride; bromine is reacted with mercurous caprylate and with mercuric palmitate yielding heptyl bromide and pentadecyl bromide (as pentadecyl pyridinium bromide) respectively; and chlorine or bromine is reacted with thallium oenanthate yielding hexyl chloride or bromide. Diluents such as air, carbon tetrachloride, chloroform or ether may be employed.

Description

Patented Oct. 17, 1939.

UNlTEi) STATES PATENT OFFICE '7 METHOD OF MANUFACTURING ORGANIC CHLORINE AND BROMINE DERIVATIVES Heinz Hunsdiecker, Clare Hunsdiecker, and Egon Vogt, Cologne-Lindenthal, Germany No Drawing. Application April 2, 1936, Serial No. 72,446. In Germany April 8, 1935 9 Claims.

As appears, however, from the method forming the subject-matter of the present invention, the reaction of the silver salts with chlorine or bromine proceeds completely diflerently, viz. according to the following equation:

There are, thus, obtained from fatty acid silver salts and chlorine or bromine, and with the splitting-off of a C-atom/ besides AgCl, or AgBr respectively, the alkyl-halides. The reaction is not restricted to the silver salts; it proceeds in the same manner also with numerous other metal salts, especially with those of the first, the second, and the third group of the periodic table of the elements.

Also the salts of substituted fatty acids react in a similar manner, in which cases always compounds poorer by one C-atom are formed.

Thus, from a hydroxy-acids, hydrogen halide compounds of the aldehydes are obtained:

From hydroxy-acids in which the hydroxyl group is not in the a position, hydroxy-alkylhalides are obtained:

From polyhydroxy-acids with one OH-group in the alpha position are obtained the hydrogen halide compounds of the hydroxy-aldehydes:

From a-halogen-fatty acids are obtained 1,1- halogenated hydrocarbons:

From n-fold halogenated fatty acids are obtained the (n+1)-fold halogenated hydrocarbons:

From dicarboxylic acids are obtained di-substituted hydrocarbon-halides:

R.(CO1Vie) 2+2H1g2- R.Hlg2+2COz-|-2M6Hlg From ester-acids are obtained the halogenfatty-acid-esters:

R +m (R.Hlg). c o o cgm+c 0:+MeHlg.

c o 0 Mo From a-keto-acids are obtained the acid halides (poorer by 1 C-atom):

R.CO.COOMe+I-I1g2 R.COHlg+CO2+MeHlg From cycloalkan-monoand -polycarboxy1ic acids are obtained the corresponding cycloalkylhalides, for example:

CHI

From amino-acids (except a-amino-acids) are obtained the halogen-alkylamines:

NH2.R.COaMIe+I-Ilga=NH2.R.H1g+CO2+MeHlg And from a-amino-acids are obtained the alkylidene-imi1ie-hydrohalides which, with H20,

decompose into aldehydes, viz:

The following examples will serve to illustrate fully the present invention:

(1). 1 mol of well-dried silver palmitate'is exposed to a current of air having a temperature of 30 to C. and being laden with bromine vapor, this process being continued until no bromine is any more absorbed. From the pasty mass the pent-adecyl bromide is obtained by subjecting the mass to pressure, or what is to be preferred, said bromide is extracted by means of ether or the like, and if desired, it may easily be purified by distillation under vacuo. The yield amounts to about to of the theoretical.

(2) 1 mol of well-dried silver laurate is transfromed into pasty state with CC14, and simultaneously therewith, or thereafter, I mol of B1: is gradually added, the mixture being now and then cooled. The further working is then e1' fected in the same manner as in the preceding example. Instead of CC14 also CHCI: or dry! ether may be used. The yield in undecyl bromide amounts to about 75 to 80% of the theoretical.

(3). 1 mol of silver acetate is subjected in a suitable vessel to a current 01' air saturated with bromine vapor, care being taken that the temperature in the reaction vessel does not become too high. The escaping gases are, by means of CuCl or the like, freed from the excess of the bromine, and the methyl bromide thus obtained is condensed in a well-cooled receiver. The yield in methyl bromide amounts to about 80% of the theoretical.

(4). Coco fat is saponified with the just sufficient quantity of dilute alcoholic sodium hydroxide, whereafter the silver salts of the coco oil fatty-acids are precipitated by means of nitrate of silver, said salts being then washed and dried. The further procedure is carried out in the same manner as in the examples 1 and 2, whereby finally as product a mixture of alkyl bromidics or carbon-chains C1-C1'1 is obtained.

It is inthis case particularly remarkable that one succeeds in this way, starting from carbonchains with an even number of C-atoms, to obtain alkyl-halides with an odd numberof C-atoms. These compounds do not exist in nature, they are not in natural products, and the chemical industry has hitherto been compelled to omit their utilization, but owing to the new conversions above disclosed this is no longer necessary, as, starting from the alkyl-halides, it is easily possible to obtain numerous important compounds. Besides, the metals are very easily quantitavely regenerable.

(5). grams of the silver salt of a-hydroxypalmitic acid are treated with bromine, as in the examples 1 and 2. After separation by means of ether, the hydrobromide of the pentadecylaldehyde which was obtained .according to the equation:

CH3. (CH2) 1s.CHOH.COOAg+Br2- CH3.'(CHa) 1a.CHO.HBr+AgBr|-CO2.

can easily be converted into a phenyl-hydrazone of Ll-dibromo-heptadecane,

(7). grams of the silver salt of the 9,10- dichioroctadecanoic acid (obtained from chlorinated oleic-acid) are well dried and pulverized finely during a comparatively long time in a mechanical mortar. Then a solution of bromine in C014 is added until no bromine is any more taken up. After having filtrated and concentrated by evaporation 1-bromo-8,9-dichloroheptadecane is obtained in the form of a darklycolored product. Yield: 13 grams.

(8). 37 grams of well-dried and pulverized silver sebacate are introduced by and by into a solution of 29 grams of bromine in dry CCl-i, the liquid becoming hot by itself and commencing to scum, so that it must now and then be cooled. The reaction product is extracted, the extract is concentrated by evaporation, and distilled under vacuo.

Yield: 15 grams. bp. 140-144 C. at 15 mm.

x (9). To 217 grams of the silver-salt of the sebacinic-mono-ethyl-ester-acid are added 110 grams or bromine, as in the preceding examples. There are obtained 126,5 grams (--75% of the theoretical) of Q-bromo-nonyl-acid ethyl-ester. Boiling-point: 118 C. at 2 mm. Hg.

(10) 10-grams of the silver salt of pyruvic acid are carefully and with very good cooling, mixed with a solution of bromine in CC14 until no bromine is any more bound. The acetyl bromide obtained according to the equation can be separated from the CCli only with difiiculty, and it is, therefore, preferably used together with it for acetylizations.

(11). 26 grams of silver mandelate are carefully and gradually mixed in dry ether with 15 grams of bromine, whereafter the ether is separated and the remaining product is concentrated by evaporation. The benzaldehyde obtained according to the formula is preferably purified by the bisuiflte compound. The yield varies, in that the hydrogen bromide arising at the same time splits partly the silver salt.

(12) 7.5 grams of glycocol are thoroughly intermixed by rubbing with 21.6 grams of precipltated HgO so as to obtain a product, the essential component of which is mercury amino acetate. 'Then a 10% solution of bromine in carbon disulphide is gradually added as long as bromine is still consumed. There escapes a regular current of CO: and of formaldehyde. The yield in formaldehyde amounts to about 60 to 80% of the theoretical.

(13). 1 mol of silver stearate is subjected to the action of dry chlorine at a gradually rising temperature (twards the end 100 C.). It is suitable to the purpose in view to interrupt the procedure from time to time, and the mass finally obtained is then thoroughly kneaded. After the pasty mass has been extracted with ether the resulting product consists nearly entirely of heptadecyi chloride. The yield depends greatly on how. well one succeeds in subjecting the entire quantity of the silver stearate possibly quickly to the action of the chlorine.

(14). grams of mercurous caprylate are mixed, at a temperature of about to C., with a solution of 35 grams of bromine in com. of C014. The CO: splitting-off takes place somewhat slower than with the silver salts. The mercurous and mercuric-bromide obtained by the then following filtration is shaken repeatedly with hot water, and there is finally obtained heptyi bromide of excellent purity. Yield: 1416 grams.

(15). 75 grams of well-dried mercuric palmitate are moderately heated and mixed in this state with a mixture of 40 grams of bromine in 150 com. of C014. When the COz-disengagement has ceased, the composition is still heated for a short period of time in a water-bath and is finally filtered and concentrated by evaporation. While this takes place, there separate mercurycontaining impurities, from which can be decanted, in order to remove further impurities, the product is distilled under vacuo. It is also possible to heat it together with pyridine for from 1 to 2 hours at a temperature of from 100 to C., then dissolve it in a small amount of alcohoi, and precipitate a pyridinium salt by means of an excess of ether. This salt contains then the entireamount of the pentadecylbromide in the W form of pentadecyl-pyridinium-bromide. 60-70% of the theoretical.

(16) i Thallous heptylate is prepared by concentrating by evaporation an aqueous solution of 1/ 10 mol of hydroxide of thallium and 1/10 mol of heptylic acid. The thallium product thereby obtained is treated with chlorine or bromine, as

Yield:

in some of the preceding examples, there being then obtained hexyl chloride, or hexyl bromide respectively, in a yield amounting to nearly 100% and being easily separable from the thallium halides by distillation.

(17) 102.5 grams of mercuric caprylate mixed 100 com. of CS2 are further mixed gradually in a flask equipped with a reflux condenser with 22 ccm. of Bra. There arises a uniform current of CO2. After the conversion has become complete the separated HgBr-z obtained by filtration is thoroughly washed with CS2. The carbon disulfide is distilled ofi with the aid of a'waterbath, and the residue is fractionated .under vacuo. There are obtained 55.7 grams of heptyl bromide having a boiling point of 74 C., said amount being 75.5% of the yield in bromide theoretically to be expected.

(18). 4f grams of dodecandicarboxylic acid are mixed with 100 com. of CC14; and then 9 ccm. of

bromine are gradually added. After the reaction has been finished, the'silver bromide is separated by filtration and washed out with hot C014.

vacuo. There are obtained 16.8 grams of 1.12-.

dibromo-decane having a boiling point of 190- 195 C. and a fusing point of 35 to 36", said amount of grams being equal to 60% of the theoretical.

We claim:

1. The method of manufacturing halogencontaining organic compounds from organic substances containing carboxyl groups, said substances being salts of metals selected from the group consisting of mercury, silver andthallium, said method comprising reacting upon said se-' lected salt in the absence of water, with a halogen chosen from the group consisting of chlorine and bromine in gaseous form, whereby CO2 and a metal halide splits oil and a mono-halogenated hydrocarbon remains.

2. The method of manufacturing organic halogen-containing compounds which comprises reacting, in the absence of water, a metal salt of a saturated fatty acid where the metal is a member of the group consisting of silver, mercury and thallium, with a substance chosen from the group which consists of chlorine and bromine, whereby the carboxylic group splits of! and is replaced by a single halogen atom.

3. The method which comprises reacting, under anhydrous conditions, a halogen of the group consisting of bromine and chlorine upon a saturated fatty acid compound which contains at least one CCOZ group, wherein Z is a member of the group consisting of mercury, thallium and silver, whereby at least one COOZ group is replaced by not more than a single halogen atom.

4. The method which comprises reacting, under anhydrous conditions, a halogen of the group consisting of chlorine and bromine upon a saturated fatty acid compound which contains at least one COOZ group, wherein Z is a metal chosen from the group which consists of silver, mercury and thallium,- whereby carbon dioxide and a metal halide split off, and leave a monohalogenated hydrocarbon.

5. The process of manufacturing saturated alkyl halogen compounds containing an odd number of hydrogen atoms which comprises subjecting a dry silver salt of an a-hydroxy carboxylic acid, whose alkyl group contains an even number of hydrogen atoms to the action under anhydrous conditions of a halogen chosen from the group consisting of bromine and chlorine until carbon dioxide ceases to escape, whereby the carboxyl group splits off and is replaced by a single halogen atom. I

6. A process of manufacturing organic halogen compounds from saturated carboxyl containing salts chosen from the group consisting of silver, mercury and thallium salts, under anhydrous conditions, which process comprises saturating said salts with a halogen chosen from the group consisting of bromine and chlorine whereby a metal halide is. formed and one carboxylic group is replaced by one halogen atom to form a monohalogenated hydrocarbon and separating and purifying said halogenated compound.

7. A method of manufacturing halogen-containing organic compounds from saturated carboxyl-containing salts of metals chosen from the group which consists of silver, mercury and thallium, which comprises completely reacting said salts under anhydrous conditions with a halogen chosen from the group consisting of chlorine and bromine, wherebycarbon dioxide and metal halide split off and are replaced by a single atom of halogen, thus forming a halogenated hydrocarbon.

8. The method of manufacturing halogen-containing organic compounds from organic substances containing carboxyl groups, said substances being salts of metal selected from the group consisting of silver, mercury and thallium, said method comprising completely reacting upon said selected salt under anhydrous conditions, with a solution of a halogen selected from the group consisting of bromine and chlorine, dissolved in a solvent chosen from the group consisting of ether, carbon di-sulfide and carbon tetrachloride, whereby the carboxyl group is replaced by a single atom of halogen, whereby a halogenated hydrocarbon is formed.

9. The method of manufacturing halogen-containing organic compounds which comprises reacting, under anhydrous conditions, salts of the metals chosen from the group which consists of silver, mercury and thallium combined with acids selected from the group consisting. of hydroxy fatty acids, poly-hydroxy fatty acids, u-keto fatty acids, a-halogen fatty acids, polyhalogen fatty acids, dicarboxylic fatty acids, acyloxy fatty acids, cyclo-alkyl monoand polycarboxylic acids and amino fatty acids thereby splitting off at least one carboxylic group and replacing it by one halogen.

HEINZ HUNSDIECKER. Mas. CLARE HUNSDIECKER. EGON VOGT.