DE1793038C3 - Process for the production of tertiary phosphines - Google Patents

Description

Setting at a temperature not exceeding ^{6O 0 C leads.}

temperature in the presence of a saturated alipha- The invention relates to a process for the production '

tables or heterocyclic ether from carbon of tertiary phosphines of the general formula

material. Hydrogen and ether oxygen as a solution (R ₂ ) »P (Ri) m by reacting sodium with a

medium is carried out. ao mixture of a halide of the general formula

2. The method according to claim 1, characterized in that R ₂ X and a phosphorus compound is generally characterized in that the halide of the general formula (RO) _n P (R ₁ ) Tn, in which

Formula R ₂ X cyclohexyl chloride, alkyl chlorides with ",., .... u- ~ a ~ - Λΐυ., ι η ,, ι n ι

2 to 3 carbon atoms, sec alkyl chlorides, chlorobenzene R ™ d R ₁ identical or different alkyl, lycloalkyl

be used. _a , or aryl groups,

3. Process according to Claims 1 and 2, characterized in that R * is an alkyl, cycloalkyl, aryl, alkoxyalkyl or that the phosphorus compound of the alkenyl group with 3 to 4 carbon atoms, general formula (RO) _n P (R ₁ ) Tn Tris-lower- X a chlorine or bromine atom,

alkyl phosphite is used. _{n is} an integer from 1 to 3 and

4. Process according to Claims 1 to 3, characterized in that 30 _{m is a number from 0 to 2} and η + m = 3, characterized in that the reaction temperature is 25 ° C

does not exceed and is preferably 0 to 10 ° C, in a solvent that is characterized by

wearing. it is shown that the reaction at a 6O ⁰ C does not

_____ excessive temperature in the presence of a

35 saturated aliphatic or heterocyclic ether made of carbon, hydrogen and ether oxygen as

From GB-PS 10 66 309 it is known to carry out pure solvents

Representation of tri - C ₁ - C ₅ -alkylphosphines, which of the halogens X becomes chlorine and of the

by Grignard reaction from C _{1 -C 5} -alkyl-Gri groups R ₂ is the cycloalkyl, the sec. Alkyl, the

standard reagent and phosphorus trihalide in ether and 40 allyl, methallyl, the C _{1 -C s} -alkyl or the aryl

inert hydrocarbons have been formed, the group has been given preference since it has been found that

reaction mixture obtained initially from which the reaction proceeds smoothly and good yields of the

rend the reaction formed Mg (Hal) ₂ - the tert in the desired. Phosphine provides one of these _{when R 2}

Form of Mg (Hal) ₂ · 6 H ₂ O is separated - and is groups. When using hydrocarbons

then rid of the ether by the trialkyl 45, however, the yields are low and in some

Phosphine by treatment with water and mineral cases even equals 0.

acid is brought into solution, from which the ether depends. It is surprising that this reaction occurs in ethers

is separated, and finally flows smoothly from the aqueous solution, since sodium alkyl and sodium phenyl

split the trialkylphosphine into ethers, as is known, by treatment with bases.

cut down and separate. This process is very un- 50 The reactants can in the stoichi

of course. metric quantities as they continue in the equation

From US-PS 32 23 736 it is known for Her- above are used. A tertiary phosphite position of tertiary phosphines has been found, however, that it is particularly expedient to react the sodium and the R ₂ X compound slightly with alkyl halide in the presence of sodium and to use the reaction in an excess of hydrocarbon but usually 10% as solvent. This procedure does not exceed. The amount of solvent is not only gives good yields if the starting point is critical. You just have to be large enough to keep the mixture of primary alkyl halides material with at least stirrable. The solvent can be used in 4 carbon atoms, it can be large excess of z. B. 51 per mole of R ₂ X-Verbinnicht on secondary or tertiary alkyl halides application can be used. But this has no advantage, alkyl chlorides with 1 to 3 carbon atoms are involved, and the recovery costs for the solvent are slow, allyl, methallyl and benzyl solvents are increased.

Halides do not react at all, and Cycloalkyl- If the reaction up to tempera halides only give low yields in carbon doors of 60 ⁰ C, the hydrogen is used as a solvent. Aromatic phos- 65 reaction temperature, preferably to room tempephine, can be produced by this previously known process (20-25 ° C) and below (eg 0 or even not in good yields and good pure -2O ⁰ C), hpitsorad. Apart from that, it was often because the temperature usually rises.

booty decreases and side reactions occur, glycol - diethyl ether, triethylene glycol dimethyl ether,

the temperature to about the lowest value ge ^ -Diethyl-U-dioxolane, 2-methyl-2-ethyl-1,3-di-

in which the reaction takes place to best eroxolane, tetraethylene glycol - dimethyl ether, cyclo-

achieve results. hexanedimethanol dimethyl ether, 1,4-cyolohexanediol

You can get smelly phosphines if you take a diethyl ether, ethylene glycol dimethyl ether and ethyre

Mixture of R, X compounds used in the lenglycol diethyl ether.

the R _r groups are different, or if the Re examples of phosphines that are produced according to the invention

Participants in the action contain an R _r group that can be provided by the trimethyl, triethyl,

Rj group of the R, X compound is different. Tripropyl, tributyl, tri-sec-butyl, triisobutyl, tri-

Examples of the (RO ^ PfROm compound are the »o t-butyl, triamyl, tri-sec.-amyl, trihexyl, tri-l-me-

tert. Phosphites, such as trimethyl, triethyl, triethylpentyl, tricydohexyl, triallyl, trimethylallyl,

butyl, trioctyl, tri-sec-butyl, tris-decyl, tri-tri-2-methylcydohexyl, tribenzyl, triphenyl, tri

phenyl-, tri-p-cresyl-, tricyclohexyl-, tri-benzyl-, 2-methyl-phenyl-, tri-3-raethylphenyl-, tri-4-methyl-

Diphenyl-decyl-, tri-xylenyl-, as well as the tri-p-butyl-phenyl-, trioctyl-, tri-1-ethyl-butyl-, tri-1-methyl-

phenyl phosphite; Phosphonites, such as diphenyl- 15 hexyl-, tri-1-propyl-butyl-, triheptyl-, tri-1-methyl · ·

phenyl-, Ο, Ο-dimethyl-phenyl-, heptyl-, tri-1-methyl-nonyt-, tris-octadecyl-, trisdecyl-, Tris-Ä-naphthyl-, tri - ^ - naphthyl-, tris- (o-meth-

OCH ₃ X oxyphenyl) -, tris (p-ethoxyphenyl) -, jricyclopentyl,

1 diethyl-phenyl-, dimethyl-phenyl-, ethyl-diphenyl-, _ao di-sec-butyl-phenyl-, diethyl-isopropyl-, diamyl-phenyl-, o-tolyl-diphenyl-, dicyclohexyl-phenyl- and that Cyclohexyldihexylphosphine.

Unless otherwise stated, it is

0,0-Dioctyl-phenyl-, 0,0-Dimethyl-aHyl-, O ₁ O-Di- all parts and percentages by parts by weight or

butyl-butyl-, 0,0-diethyl-butyl-, O.O-dimethyl-cyclo- »5 percent by weight.

hexyl and 0,0-dipropyl-methyl-phosphonite; The method of the invention is carried out by the following

Phosphinites, as illustrated by the O-methyldiphenyl, O-phenyl- genden examples,

diphenyl-, O-butyl-dibutyl-, O-ethyl-dimethyl-, 0-Me-.

ethyl-dicyclohexyl- and O-ethyl-dimeth-allyl- Example 1

phosphinic 30 A solution of 86 g of isopropyl chloride and 93 g

_ Examples of R _a X compounds are methyl, triphenyl phosphite was added dropwise to 51 g of sodium in

Ethyl, isopropyl, n-propyl η-butyl, sec. Butyl, dibutyl 500 cc at 50-55 ⁰ C. The reaction

Cyclohexyl, allyl, methallyl, cyclopentyl, 2-mixture was still 1 hour after the end of the

thylcyclohexyl and benzyl chloride, the chlorine addition is stirred, then water is added and the

benzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 35 organic layer separated. The dibutyl ether

p-chlorobutylbenzene, the octyl, t-butyl, amyl, layer resulted in the fractionation 60 g of pure tri-

sec. Amyl and hexyl chloride, 2-chlorohexane, isopropylphosphine. Bp 170-175 ° C.

3-chlorohexane, 2-chloroheptane, 4-chloroheptane, heptyl-. . ,

chloride, 2-chlorooctane, 2-chlorodecane, a-naphthyl- ^ Example I.

chloride, / J-naphthyl chloride, 2-chloroanisole, the lake. 40 84 g of ethyl chloride were added dropwise together with 37 g

Butyl, allyl, cyclohexyl and methyl bromide, trimethyl phosphite to 51 g of sodium, dispersed in

the octadecyl and decyl chloride. Tetrahydrofuran, at 20-25 ° C. After adding

In the case of the ethers that are used as solvents, water is used for hydrolysis, separating the organic ones

the can, it is a saturated aliphatic layer and fractionation resulted in 18 g (50%

and saturated heterocyclic ethers with rings of 45 yield) pure triethylphosphine. Bp. 128 ⁰ C.

more than 4 carbon atoms. For this, _n . . . ,

cyclic acetals and ketals can be used. Des- Example 5

same can ethers of glycols and polyoxy- A solution of 65 g of cyclohexyl chloride and 46 g

alkylenes can be used. Trimethyl phosphite was added to 26 g of sodium, dispersed

Examples of suitable ethers are butyl ethyl, 50 gated in dibutyl ether, at 20-25 ° C. After hydrolysis

lake. Butyl-ethyl-, t-butyl-ethyl-, ethyl-isoamyl-, iso- with water and separation of the organic layer

butylethyl, ethyl-t-amyl, butylisobutyl, butyliso- were added an aliquot to carbon disulfide

propyl, butylmethyl, see. Butylmethyl-, 2-methyl- too, to become a permanent adduct of phosphine

butyl-methyl-, t-butylmethyl-, isoamylmethyl-, butyl- form. The tricyclohexylphosphine was in 90%

propyl, isoamylpropyl, cyclohexylmethyl, dibutyl, 55% yield.

Di-sec.-butyl-, Diisoamyl-, Butylisoamyl-, diethyl-, Increasing the temperature to 50 C since ^e-Diheptyl-, dihexyl, diisopropyl, dimethyl, dioctyl down against the yield of tricyclohexylphosphine to tyl- , Diamyl, dipropyl, ethylheptyl, ethylhexyl, 45-50%. If, for comparison, the dibutyl-ethylisobutyl, ethyl isopropyl, ethylmethyl, amyl ethers were replaced by aliphatic hydrocarbon solution ethyl, ethylpropyl, heptylmethyl, isobutylmethyl, 60-isopropyl, isopropyl-propyl, isopropyl-propyl-isopropyl-isopropyl, the tricyclohexylpro- isobutylphosphine was found 30-35%,
Methylamyl, dicyclohexyl and methylpropyl example 4
ether, tetrahydrofuran, 2-methyltetrahydrofuran, di-

ethylene glycol-diethyl ether, diethylene glycol-dimethyl-3 mol of chlorobenzene in a mixture with 1 mole Triäther, 1,4-dioxane, 1,3-dioxane, 1,3-dioxolane, 2-Me 65 methyl phosphite was added at 0-10 ⁰ C. to 6.2 g of sodium 1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2,4-di-trium, dispersed in 700 ecm of dibutyl ether. After Bemethyl-IS-dioxane ^^ - Dimethyl-IS-diojian ^ methyl end of the addition, the reaction 1,3-dioxane, propylene glycol dimethyl ether, dipropylene mixture was washed with water and subjected to the organic

5 6

Layer of distillation. The yield of pure triphenyl phosphite in the presence of hydrocarbon

phenylphosphine was 240 g (91% of theory). solvents and sodium.

In contrast, there is no reaction of the chlorine. . . _

benzene and trimethyl phosphite in benzene or example /

Heptane below 60 ⁰ C instead, the yields of 5 277.5 g (3 mol) butyl chloride and 310 g (1 mol) tri-

the desired product is decreased, and phenyl phosphite was manbei 0-10 ⁰ C to 138 g Na

there are increasing amounts of ertrium impurities, dispersed in 11 ethylene glycol formal (1,3-di-

keep. oxolane), following the procedure given in Example 1

ρ., · ._ · ι ^ Work-up of pure tributylphosphine in good

ίο loot received.

275 g (3 moles) see. Butyl chloride and 310 g (1 mol) R _P i ς η i ρ 1 8

Triphenylphosphite was added at 0-1O ⁰ C to 138 g ^p

Sodium dispersed in 800 ecm dibutyl ether. The 379.5 g (3 mol) of benzyl chloride and 310 g (1 mol)

The product became triphenyl phosphite in the manner indicated in Example 1 and was added at 5-10 ^° C. to 138 g

worked up further, with pure tri-sec-butyl-15 sodium, dispersed in 1.5 l of tetrahydrofuran, with

Phosphine was obtained in yields which are much greater than those obtained after the work-up indicated in Example 1

were those obtained in good yields using pure tribenzylphosphine.

Hydrocarbon solvents. In the presence of hydrocarbon solvents

and sodium reacted against the benzyl chloride

Examples ^ao not at all with the triphenyl phosphite.

219.5 g (3 moles) allyl chloride and 310 g (1 mole) tri Example 9

phenyl phosphite was added 2.13 mole of ethyl chloride, 1 mol Ο at 10-15 ⁰ C to 138 g Na, Ο-dimethyl-phe

trium, dispersed in 900 ecm diethylene glycol dinylphosphite and 4.27 g sodium atoms in 500 ecm methyl ether, and after further work-up 35 dibutyl ethers were reacted at 10-15 ° C and that

in the manner indicated in Example 1, pure triallyl product in the manner indicated in Example 1 further

phosphine was obtained in good yield. In contrast, worked up, using pure diethylphenylphosphate

in addition, allyl chloride did not react at all with triphine as the end product.

Claims (1)

_ "" ", Only when applying significantly increased Tempe patent claims. smoke at all possible, this reaction in coal 1. Process for the production of tertiary Phos hydrogens carried out as solvents, wherein phinen of the general formula (R ") nP (Ri) m by correspondingly low yields of the desired Reaction of sodium with a mixture of a 5 phosphines can be obtained. 'Halides of the general formula R ₈ X and a The invention is based on the knowledge that one Phosphorus compound of the general formula also does not apply to this previously known process (RO) _n P (ROm, in which R and R _{1 are available in the} same or in insufficient or only in unsatisfactory yields various alkyl, cycloalkyl or aryl groups, tertiary phosphines, such as the phosphines with C ₁ - C ₃ - R _{t is} an alkyl, cycloalkyl, aryl, alkoxyalkyl ίο alkyl, with sec. Alkyl, with allyl, methallyl, with or alkenyl groups with 3 to 4 carbon atoms, X a cycloalkyl, with aryl groups using the Chlorine or bromine atom, π an integer from 1 to previously known reaction obtained in good yields 3 and m are an integer from 0 to 2 and can, if you use as a solvent instead of Koh- n + m = 3, in a solvent that uses saturated aliphatic ethers characterized in that the environment i§ det and the reaction below 6O ⁰ C by-