DE892595C - Process for the production of organic halogen compounds - Google Patents

Description

(WiGBl. P. 175)

ISSUED OCTOBER 8, 1953

N 4330 IVc 112

The invention relates to improvements in the production of organic halogen compounds, especially unsaturated aliphatic compounds Connections that are often difficult or expensive to make. The difficulty and the high price are particularly found in organic jbdiden, and it is an aim of the present Invention to provide a process by which a variety of organic halides produced remarkably easily and in many cases cheaper than conventional processes can be.

The present method consists in that one an alkyl, alkylaryl or aryl phosphk with an organic halide and an organic oxide compound. (The reaction given in runs smoothly and in high yields in many cases, leads to organic halogen compounds corresponding to the organic oxydiverbinduing used as the starting material in which the oxy group is replaced by a halogen atom.

The organic halide can be an alfcyl halide or an aryl halide or an organic halogen ester, e.g. ethyl bromoacetate. Since organic iodides are often more difficult and expensive to manufacture, the invention is special valuable when the organic halide is an iodide.

The organic halide can contain more than one halogen atom in the molecule and e.g. B. carbon tetrachloride ¹ or ethylene diferomide.

When the phosphite reacts with the organic. Halide can · if the in the reaction resulting organic halogen compound

has a reactivity that of organic Halides is comparable to mixtures of products resulting from a further implementation of the reaction product with the phosphate come. The organic halide must therefore be selected so that it has a greater reactivity to the phosphate than that Reaction product. In this way, side reactions are avoided or to a minimum ίο reduced. The reaction was among those Conditions run apply that the organic halagen-containing reaction product removed from the reaction mixture according to its formation will. For example, the temperature conditions and the organic halide can be chosen so that the organic halogen-containing Reaction product, as soon as it is formed, from the Reiaktionsgeniisch lab distilled. In some cases is the reaction product at the reaction temperature inconsistent, e.g. B. tertiary butyl iodide decomposes with elimination of hydrogen iodide to isobutylene.

It should be noted that since the phosphites are hydrolyzed in the presence of water, it is desirable is to exclude water from the reaction mixture in order to hydrolyze the: phosphites avoid or minimize them. In view of the easy accessibility of the Triaryl phosphites is the invention preferably using the triaryl phosphites, in particular using trialkyl phosphites, carried out, especially with the trialkyl phosphites the possibility exists that the well-known Arbusov reaction takes place, which involves the exchange of alkyl groups of the phosphites with the organic residue of the organic halides' Covers.

It is possible that phosphite-alkyl halides are temporarily formed as intermediates in the reaction, which with the organic Oxy compound react to form the desired organic halogen compound. from Triphenylphosphite methiodide is one such possible temporary intermediate already well-known connection and! was won. The invention therefore also includes manufacture of organic halogen compounds through reaction of alkyl, alkyiaryl or arylphosphital alkyl or aralkyl halides with an organic oxy compound. Said alkyl halide is preferably a triaryl phosphite methiodide. This reaction is common in normal Temperatures incidentally, and the reaction is therefore preferably below in such cases strong cooling of the reaction mixture carried out, although in some cases gentle heating of the reaction mixture may be required can if the reaction · at ordinary room temperature is not fast enough.

Aliphatic alcohols are used, though other oxy compounds are also useful, and if the aliphatic alcohol is unsaturated so the reaction product is an unsaturated halide.

It must be pointed out that in addition to the organic Halogenverfoindüngen ^ which are produced, the original phosphorus compound in the form of diaryl, dialkyl or diaralkylalkane or aralkane phosphonates ". These phosphonates are valuable in itself as ancillary compounds for the production of other phosphorus-containing compounds, or they are also · in many cases direct themselves valuable as a plasticizer.

To control the course of the reaction in carrying out the present invention of the reactions too explain the following equations. If the process is in one step from trialkyl phosphite and an alcohol and an organic halogen compound applies the equation (I). '

(R0) ₃ P + R'0H + R "Hal ^ (RO) ₂ PO-R"

+ ROH + R'Hal

(I)

. (RO) 3P + R "Hal - ^ (RO) ₃ PR" Hal (II)

(R 0) 3 PR "Hal + ROH - ^ (RO) ₂ P 0-R" + R0 (H + Ä'Hal ((HI)

If the process is carried out as a two-step process, equations (II) apply and (III).

In the equations, R, R 'and R "denote organic radicals and Hal 1 denotes a halogen atom.

The following examples illustrate the manner in which the invention can be practiced.

example 1

A mixture of 31 g triphenyl phosphite, 28.4 g methyl iodide and 4.6 g ethyl alcohol was heated on the steam bath for 60 hours. At the end of this time the reaction mixture was distilled, and rag Äthyljöd'id were recovered equal to a yield of about 77 ⁰ Zo of theory.

Example 2 ₁₀ _

A mixture of 3.Γg triphenyl phosphite, 14.2g methyl iodide and 7.4 <g. Butyl alcohol was heated under reflux for 18 hours on the steam bath and then distilled to give 17 g of slightly contaminated n-butyl iodide, corresponding to a yield of a little over 0.08%. Redistillation gave 14 g of pure n-butyl iodide with a boiling point of 130 to 131 °.

Example 3

A mixture of 34 g of triphenyl phosphite, 7.4 g of sec-butyl alcohol and 21 g of methyl iodide was refluxed for 39 hours. The distillation gave 24 g of crude product which, on fractionation, gave 12.2 g of sieved butyl iodide, corresponding to a yield of about 66 %.

At game 4

A mixture of 10 g triphenylphoisphite, 10 g Methyl iodide and 4 g sec-nr-octyl alcohol were refluxed for 24 hours. The distillation

yielded 7 g of 2-iodoctane, corresponding to a yield of 94.8%.

For example 5

A mixture of 34 g of triphenyl phosphite, 21 g of methyl iodide and 10 g of cyclohexanol was refluxed for 48 hours, the temperature of the mixture from 75 to no ° ^; was increased. Distillation with subsequent washing with water, drying and fractionation of the product gave 8.5 g of cyclohexyl iodide, which corresponds to a yield of 41.7%.

Examples

34 g of triphenyl phosphite, 21 g of methyl iodide and 5.8 g of allyl alcohol were refluxed for 48 hours heated. Distillation with subsequent washing of the product, drying and fractionation resulted in a fraction boiling at 80 to 10 °, which consists of a mixture of methyl and. AUyI-iodides consisted, and 8 g one from ιοί to 103 ° boiling fraction consisting of allyl iodide. The overall yield of allyl iodide: determined by the determination of the refractive index of the two fractions was calculated to be about 71.5%.

Example 7

A mixture of 34 g triphenyl phosphite, 21 g methyl iodide and Γ2.2 g ^ -phenylethyl alcohol was refluxed for 48 hours. The reaction product was mixed with 100 ecm of ethyl ether and washed several times with cold, dilute sodium hydroxide solution and dried over sodium sulfate to which a little sodium bicarbonate had been added. The distillation of the product under reduced pressure gave 23 g / J-Phenylathyljodid, which corresponds to 94-95 ⁰ mm under a pressure of 1.5 boiled and a yield of 99% of a product with 95 to 98% purity.

Example 8

A mixture of 62 g triphenyl phosphite, 28 g methyl iodide and 7.6 g dimethyl glycol was added heated in the steam bath for 30 hours. After distilling, - washing with dilute sodium hydroxide solution and water, drying and fractionation of the product, 116 g of trimethylene iodide were obtained, which corresponds to a yield of 55%.

B e i s ρ i e 1 9

A mixture of 68g triphenyl phosphite, 42g Methyl iodide and 10 g of 2,2-dimiethylene trimethylene glycol was refluxed for 319 hours. The 'product was mixed with 200 ecm of ethyl ether and washed three times in succession with 5 percent by weight aqueous sodium hydroxide solution, then dried and fractionated. 27.5 g of 1,3-diiodo-2,2-dimethylpropane were obtained, which corresponds to a yield of about 88%.

Example 10

A mixture of * 34 g triphenyl phosphite, 21 g methyl iodide and V2 g ethyl acetate was under

Heated to reflux at a temperature gradually increased from 75 to 115 ° for 48 hours. The product was distilled, washed with water, dried, and fractionation gave 17.5 g of ethyl os-iodopropionate, which corresponds to a yield of yy %.

Example 11

68 g triphenyl phosphite, 40 g n-bnityl iodide and 6.2 g of dry methanol were in the course of 24 hours to an increasing from 165 to 185 ° Temperature heated. Methyl iodide was passed through a tripod column with Fenske rings was filled, removed, wherein 'the distillation temperature did not exceed 41 °. 20 g of product were obtained, which after washing with water, drying and distillation gave 16> g of methyl iodide, which corresponds to a yield of about 56%.

Example 12

A mixture of 30 g of triphenylphosphite, 5 g of carbon tetrachloride and 7.4 g of n-butyl alcohol was heated under reflux for 16 hours on the steam bath and then ^{distilled to obtain X} 4> 5 g of a mixture of carbon tetrachloride and n-butyl chloride . By determining the refractive index of the mixture, the yield of butyl chloride was determined to be about 30% of theory.

Example 13

A mixture of 31 g triphenyl phosphite, i> 2.6 g Benzyl chloride and 7.4 g of n-butyl alcohol were heated to a temperature of 140 to 150 ° for 64 hours heated. The distillation of the product with subsequent washing with water, drying and Fractionation gave 6 g of n-butyl chloride, which corresponds to a yield of about 65%.

Example 14

A mixture of 30 g of triphenyl phosphite, 15 g of carbon tetrachloride and 10 g of n-hexyl alcohol was heated ■ 610 hours to a temperature of 150 ^0th Fractionation of the reaction mixture gave 2 g of n-hexyl chloride.

■ Example 15

A mixture of 34 g of triphenyl phosphite, 14 g of benzyl chloride and 5.8 g of allyl alcohol was heated for 48 hours at an initial temperature of 1401 ^0th The temperature dropped to 125 ⁰ as soon as allyl chloride was formed and began to distil under reflux. Distillation of the reaction mixture gave 4.5 g of allyl chloride, which corresponds to a yield of 59%. The yield due to loss of allyl chloride by volatilization from the reaction mixture was lower than might have been expected.

Example 16

A mixture of 68 g triphenyl phosphite, 28 g benzyl chloride and 7.6 g trimethylene glycol was made Heated to 170 to 180 ° for 48 hours. The Destil-

! ation of the product with subsequent washing with dilute sodium hydroxide solution, then with water and drying and subsequent fractionation resulted 9 g of i, 3-dichloropropane, which gives a yield of 69% corresponds.

Example 17

A mixture of 34 g triphenyl phosphite, 10 g benzyl chloride and 9 g ethyl acetate sore 60 hours heated to a temperature of 175 to 180 °. During the distillation under reduced pressure, the reaction product gave 8 g of ethyl ct -chloropropionate, which corresponds to a "yield" of 76.8%.

Example. τ8

· A mixture of 26 g of triphenyl phosphite, 15 g Äthylendiibromid and 6.2 g of n-butyl alcohol was heated 60 hours at 1150 ^0th The reaction mixture was then distilled and gave a mixture of ethylene dibromide and butyl bromide, which after the determination of the refractive index. Butylibromide contained in a yield of about 40% of theory.

Example 19

A mixture of 34 g of triphenyl phosphite, σβ, 8 g of benzyl bromide umd 7.4 g of n-butyl alcohol sore heated under reflux at 140 ⁰ 46 hours, whereby 13 g of n-butyl bromide from dam Reaktionsgemiisch obtained wounds ..

Example 210

A mixture of 34 g of triphenyl phosphite, 18.8 g and 5.8 g allyl alcohol Ben'zylbromiid wutrde 48 hours under reflux, the temperature from the initial value ⁰ 140 fell to 130 °, began to distill as Allylibromid under reflux. The distillation of the product gave SgAllylbroimid ¹ , which corresponds to a yield of 66%.

Be r s ρ i e 1 21

A mixture of 68 g of triphenyl phosphite, 37.6 g of benzyl bromide and 7.6 g of trimethylene glycol was heated for 48 hours at 130 ^0th Fractionation gave 16.3 g of 1,3-dibromopropane, and further ι g of this compound was. Washing of the other fractions with dilute sodium hydroxide solution and water with subsequent drying and redistillation obtained. A total yield of 17.3 g of 3-dibromopropane was obtained, which corresponds to a yield of about 85%.

Example 22

A mixture of 34 g triphenyl phosphite, 83.8 g Benzyl bromide and 1: 1 g of ethyl acetate sore for 62 hours heated to 160 °. The product is distilled, mixed with 50 ecm of ethyl ether and diluted with Washed caustic soda and water. On drying and distillation, 13.5 g of ethyl α-bromopropibnate were sore obtained, which corresponds to an output of approximately 86%.

B e i β. ρ i e 1 23

A mixture of 50 g triphienyl phosphite and di g n-butyl alcohol was weighed into a three-necked flask fitted with a thermometer, a condenser and an inlet tube with a glass frit. Gaseous methyl bromide wound was introduced into the liquid through the tube with the glass frit for 12 hours. The temperature fell from 155 to 135 ⁰ as soon as Oj-butyl brpmide began to distill under reflux. The reaction product was fractionated twice and gave 13 g of n-butyl bromide, which corresponds to a yield of 63.4%.

The following examples explain the application of the invention using phosphite methjodide.

(Example 24

4.6 g of ethyl alcohol were added to 45 g of triphenylphosphite methiodide in an ice-cold flask. A rapid reaction occurred which was complete within 20 to 30 minutes. During the distillation of the reaction mixture, 12 g of ethyl iodide were obtained, which corresponds to a theoretical yield of y / y / o.

Example 25

21 g of isopropyl alcohol became 10 g of triphenylphosphite methyadide put in an ice-cold flask. A severe reaction occurred which resulted in about 20 to 30 minutes' ended. The reaction mixture was then distilled in vacuo, washed with water and recovered again distilled from 2.8 g of isopropyl iodide, which corresponds to 75% of the theoretical yield.

Example 26

4 g of η-butyl alcohol were added to 26 g of triphenylphosphite methiodide and the reaction mixture was left to stand for 30 minutes at room temperature. That. The mixture was then distilled under reduced pressure, 9 g of crude product being obtained, which after washing three times with water, drying and distilling gave 7.7 g of n-butyl iodide, which corresponds to a yield of 72.2%.

Example 27

6 g of sec-butyl alcohol became 33 g of triphenylphosphite methiodide given. The reaction was over after 2 hours at room temperature, and that During the distillation, the product gave T2 g of crude halide, after washing with water and drying over anhydrous potassium carbonate with Subsequent distillation gave 8 g of sec-butyl iodide, which correspond to a yield of about 60%.

As of ρ iel 28

7.4 g of tert-butyl alcohol resulted in 42 g of triphenylphosphite methiodide given and the mixture

heated to 50 to 6o) ° and kept at this temperature for ι hour '. During the distillation were then 17.5 g of crude tert-butyl iodide are obtained, which with careful cleaning by washing with ice-cold Water, drying and fractionation of the almost pure tert-butyl iodide gave. The estimated The yield of tert-butyl jadide was about 76%.

Example 29

6 g sec-n-octyl alcohol were converted into 26 g diphenyl

phosphite methiodide added, and the mixture was heated to 50 ° for 20 hours. The distillation of the mixture yielded 11.2 g · 2f-j0dootane, which correspond to a yield of 80%.

Example 30

10 g of cyclohexanol was added to 43 g of triphenylphosphite methiodide and the mixture was allowed to stand for 18 hours. Distillation of the mixture under reduced pressure followed by washing with water, drying and refractionation under reduced pressure gave I ¹ S 'g of cyclohexyl iodide, boiling point 6 °, under a pressure of 8 mm, corresponding to a yield of about 75%.

Example 31

4.8 g of crotyl alcohol became 30 g of triphenylphosphite methiodide 'given in a bottle dipped in an ice bath. A lively one Reaction occurred and after 30 minutes the reaction mixture was distilled in vacuo, which Distillate washed with Wasiser ·, and this were 10 g of crotyl iodide obtained, corresponding to about 83 per cent of theory.

B e i s ρ i e 1 32

5 g of allyl alcohol was added to 24 g of triphenylphosphite methiodide ¹ and the mixture was cooled in an ice bath. After 30 minutes, the reaction mixture was distilled, washed with water, dried and distilled again and gave 7.5 g of allyl iodide, corresponding to a yield of about 84%.

Example 33

10 g of benzyl alcohol became 42.5 g of triphenylphosphite methiodide given. The product was distilled after standing for 1 hour, washed with water, dried and then crystallized to give 19.5 g of benzyl iodide, which is a yield of about 95%.

Example 34

9 g of phenylethyl alcohol were added to 36 g of triphenylphosphite methiodide, and the product was distilled after standing for 1 hour. The distillate was dissolved in 55 ecm of ethyl ether and washed several times with dilute aqueous sodium hydroxide solution then with water, then dried and distilled. 6g / J-Phenyläthyljodid, 115 ⁰ under a pressure of up to 12 mm na boiling at iiiibi "were combined with 13 g of a slightly impure fraction was obtained. The total yield of the desired iodide was estimated to be about 70% after determining the refractive indices of the various fractions.

Example 35

Γ2 g of phieinylmethylcarbinol were added to 42 g of triphenylphosphite methiodide. After 1 hour standing, the product was worked up as in Example 7. In the distillation of a-Phenyläthyljodid were obtained 6 g, boiling point 70 'ig under 2 mm pressure, and a further fraction of 10, boiling point' ⁰ to 75 at 75 to 8o ° under 21 mm pressure. The combined fractions correspond to a yield of approximately 70%.

T) · · 1 / -

Example 36

4 g trimethylernglycol wounds ku 50'g triphenylphosphite methiiodide given. After standing for 2 hours, the product was distilled, and the distillate was washed with dilute sodium hydroxide solution, dried and fractionated, 14.8 g of trimethylene iodide being obtained wounds, which correspond to a yield of about 96%).

B e i a ρ ie 1 37

log 2,2-dimethyltrimethylene glycol wounds too 96 g of triphenylphosphite methjoidide and 10 ecm of dry ethyl ether added. The mixture was heated under reflux for 3 minutes, whereupon the product was distilled with dilute sodium hydroxide solution and washed with wasiser wound. On drying and fractionation, 17 g were then obtained of an impure 1, 3-diiodo-2, 2- <diimethylpropane obtained, which correspond to a yield of about 46%.

As already mentioned, trialylphosphites react with alkyl halides to form halides in which an alkyl group of the phosphites against, © ine alkyl group of the organic halide according to the Anbusov reaction exchanged wind. The following example illustrates the use of a trialkyl phosphite in the process according to the present invention, which leads to the formation of a mixture of iodides.

For example 38

A mixture of i6, ß g Triäthylphospbit '.14,2 g Methyljodtid ¹ and 22.2 g of n-butyl alcohol sore refluxed ι hour ioo °. Fractionation of the reaction mixture with subsequent removal of the butyl alcohol by washing with water gave a mixture of 10 g of ethyl iodide together with 8 g of n-butyl iodide.

Example 39

18 g of ethyl lactate became 70 g of triphenylphosphite methiodide given and left to stand overnight at room temperature. According to the detail

lation, washing and drying over sodium sulfate with subsequent fractionation, 32 g of ethyl criodopropionate were obtained, which corresponds to a yield of about 92%.
5

Example 40

9.5 g of cholesterol were mixed with 12 g of triphenylphosphite methiodide and 10 ecm of methyl iodide were added. The mixture was refluxed ^{for 1 hour:} at a temperature of 50 to 60 ° and then left to stand overnight at room temperature. The reaction product was extracted with petroleum ether and the solvent evaporated. The residue was washed with water and then with a small amount of acetone, whereupon it was dissolved in 2100 ecm acetone and cooled. A total of 3.6 g of cholesteryl iodide is obtained, which corresponds to a yield of about 30%.

Example 41

¹ by heating 31g TriphenylphoBphit with 30 Benzykhlorid g for 60 hours at a temperature of 170 bis 175 ° sore intermediate Triphenylphosphitbenzykiuorid! obtain.

This connection was made twice with etrolether washed, leaving 25 g of a thick syrup. 5.5 g of n-hexyl alcohol were added, and the mixture became after standing for 30 minutes distilled. The distillate was diluted with

30. Washed sodium hydroxide solution and water. On drying and fractionation, o ^ gn-hexyl chloride were obtained, which correspond to a yield of about 88%.
The present invention offers the advantage that the triaryl phosphites can be produced easily and cheaply from phosphorus hydroxide and the corresponding phenol. With the easy to manufacture and relatively inexpensive iodides, such as methyl iodide, organic iodides can thus be produced which are difficult and expensive to produce in any other way.

Claims (6)

PATENT CLAIMS: Ii. Process for the production of organic halogen compounds, characterized in that that one alkyl, alkylaryl or aryl phosphites with organic mono- or polyhalogeaidia and organic oxy compounds and ■ the resulting organic halogen compound removed from the reaction mixture, or that you first a phosphate with an organic Halide converts to an alkyl, alkylaryl or arylphosphife-alkyl or -aralkyllialogenid and then these intermediate products with an organic oxy compound, if necessary 'at a slightly higher temperature, or under strong Cooling · lets react. 2. The method according to claim 1, characterized in that that as organic halides, alkyl or aralkyl halides or an organic Turn halogen esters used. 3. The method according to claim 1 to 3, characterized characterized in that the resulting organic 'halogen compound from the reaction mixture is removed to the extent of their formation. 4. Method according to one of the preceding Claims, characterized in that. the reaction under essentially anhydrous Conditions is carried out. 5. Method according to one of the voirfiergoing Claims, characterized in that the organic oxyvene bond is a saturated one or unsaturated aliphatic or cycloaliphatic alcohol is used. 6. The method according to claim> r to 5, characterized marked that one. as an organic oxyvene bond an organic oxycarboxylic acid ester is used.