DE2758473A1 - PROCESS FOR THE MANUFACTURING OF BUTANDIOL OR SUBSTITUTED BUTANDIOLS - Google Patents

Description

Process for the production of butanediol or substituted butanediols.

The invention relates to a process for the production of butanediol or substituted butanediols, being an allylic alcohol, carbon monoxide and hydrogen in the presence of a Brings khodium carbonyl catalyst into contact with one another, being a triorganophosphorus modifier with at least incorporated an alkyl substituent.

It is known that allyl alcohol is used as a substrate for hydrof oi mylierungsreakt ion can serve and Hydroxyaldehydprodulcte supplies. Journal of the American Chemical Society, 22 »333 (1943) and 21. 3051 (1949) (Adkins and Krsek) is the synthesis of 4-hydroxybutyraldehyde in 30% yield by the cobalt carbonyl-catalyzed Hydroformylation of allyl alcohol is described. In Tetrahedron Letters 1969, (22), pages 1725-6 and Journal of the Chemical Society (A), 1970, pages 2753-64 (Brown and Wilkinson) is the hydroformylation of allyl alcohol and a number of other olefins in the presence of hydridocarbonyltris- (triphenylphosphine) -rhodium- (l) described as a catalyst that delivers the corresponding aldehydes. In the US Pat. No. 3,917,661 (Pruett and Smith) describes a process for the preparation of oxoaldehydes from olefins, wherein: a rhodium carbonyl catalyst system used by Triorganophosphorus ligand is modified, which one from the

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from trialkyl phosphites, tricycloalkyl phosphites, triaryl phosphites and triarylphosphines.

The I) T-PS 2 538 364 (Schimizu) describes a process whereby allyl alcohol is converted into an aldehyde mixture by hydroformylation in the presence of a rhodium carbonyl catalyst which is modified by any compound of a number of triorganophosphorus ligands, and wherein the Separating aldehydes by aqueous extraction and converting them to butanediol by a separate conventional hydrogenation method.

In U.S. Patent No. 3,239,566 (Slaugh et al) describes the use of phosphine / rhodium complex catalysts is described in Oxoreaktionen that produce aldehydes and / or alcohols at temperatures of, for example, 195 G ^0.

Completely unexpectedly it was found according to the invention that one under the influence of a Hhodiumcarbonylkatalysator, which by a triorganophosphorus ligand is modified, which itself carries at least one alkyl substituent, allylic Convert alcohols to butanediol or substituted butanediols in a one-step hydroformylation / hydrogenation sequence can. In the case of allyl alcohol, the desired 1,4-butanediol as a product of various amounts of 2-methyl-1,3-propanediol, Accompanied n_-propanol and i-butanol, as in equation 1 shown:

HRh (GO) (PR,) (1) CH ₂ = CHCH ₂ OH + CO + H ₂ ~ 2_JL * HO (CH ₂ ) ₄ OH

+ HIGH ₂ CHCH ₂ OH CH ₅

+ CH ₃ CH ₂ CH ₂ OH

₃ ) ₂ CHCH ₂ OH

Intermediate products of hydroformylation such as 2-hydroxytetrahydrofuran, 4-hydroxybutyraldehyde, 2- (hydroxymethyl) -P * opion.aldehyd, Propionaldehyde and isobutyraldehyde in

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of the product mix, if you look at the procedure before Termination interrupts.

When using methallyl alcohol as a substrate, the main product is 2-methyl-1,4-butanediol, which is due to lesser proportions is accompanied by 2,2-dimethyl-1,3-propanediol and isobutanol, as shown in equation 2:

(2) CH ₂ = CGH ₂ OH + CO + H ₂

HRh (GO) (PR,)? ^H 3

GH,

CII3 ₂ GCH ₂ OH

CH ₅ + (CH ₃ ) ₂ CHCH ₂ OH

The method according to the invention can be carried out in a manner that for rhodium carbonyl catalyzed hydroformylation methods is typical, with the exception that you prefer a triorganophosphorus coligand with at least one alkyl or Cycloalkyl substituents used as the commonly used triarylphosphine or triorganophosphite co-ligands. The catalyst can be in situ from elemental rhodium, rhodium oxide or rhodium trichloride (if necessary on a inert carriers such as carbon) or from rhodium carbon! compounds such as hexarhodiumhexadecacarbonyl / Rhg (CO)., g7 in contact with a suitable phosphine derivative, Carbon monoxide and hydrogen, or it can be added in the form of a hydridocarbonyl rhodium compound, e.g. Hydridocarbonyltris- (tri- £ -butylphosphine) -rhodium- (I). One can use known methods for the preparation of phosphine-modified Rhodium carbony catalysts for hydroformylation according to the invention use.

The triorganophosphorus component of the catalyst can be represented by the following formulas:

I. R ₁ -PR ₃

R ₂

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II R--R--R

Rp Rp

III. R ₁ -PR ^ -PR ₁

\ _R /

^R 4

in which the radicals R ₁ , R ₂ and R, independently of one another, are selected from the group consisting of C ₁ o _Q -alkyl-, C _1-20 -AIkOXy-, C ~ «« -cycloalkyl-, Cg_ ₂₀ -aryloxy-, Cg_ ₂₀ - aryl, C _"2Q alkaryl and C ₇ _ ₂₀ aralkyl radicals selected and their mixtures group consisting of: The radicals

e leftovers

j are independently selected from the group consisting of C, ₂₀ -alkylene-,

Cj_ ₂₀ cycloalkylene, C ₆ _ _2Q arylene, C ^ _ ₂₀ -Alkarylen- and C "is selected ₂₀ -Aralkylenresten existing group; where at least one of the radicals R (R ₁ , R ₂ , R ₃ or R ₄ ) is an alkyl, cycloalkyl, alkylene or cycloalkylene radical. Of course, these radicals can carry substituents which do not interfere with the catalyst activity.

Examples of agents used as a triorganophosphorus component of the Suitable catalyst are tri-n-butylphosphine, tri-noctylphosphine, Triethylphosphine, phenyldiethylphosphine, methyldiphenylphosphine, o-methoxyphenyldiethylphosphine, diethylmethoxyphosphine, Diethyl (4-hydroxy-n-butoxy) phosphine, 1,2-di (phenylmethylphosphine) ethylene, 1,4-diphenyl-1,4-diphosphacyclohexane, tricyclohexylphosphine, diethyl (methoxymethyl) phosphine and triisobutylphosphine. Preferred triorganophosphorus co-ligands are tri-n_-butylphosphine, tri-n-octylphosphine, triethylphosphine and phenyl diethyl phosphine.

The triorganophosphorus complexing agents according to the invention can they are also used in admixture with other agents known in the art as modifying ligands for metal carbonyl compounds are known, especially those that are catalyzed by rhodium carbonyl Hydroformylation methods used. These can include complexing agents such as triphenylphosphine, Triphenyl phosphite, triphenyl arsine, triphenyl antimony, Trimethyl phosphite, tri-n-propyl phosphite, tri- (4-hydroxybutyl) -

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phosphite, diphenyl sulfide, tri- ε -tolylphosphine, triphenylphosphine oxide etc.

The allylic alcohols of the present invention include all allylic alcohols Alcohols, i.e. compounds that are characterized by the basic structure of allylic alcohols:

C = C - C - OH

Examples of suitable allylic alcohols are allyl alcohol, Methallyl alcohol, crotyl alcohol, cinnamon alcohol, 2-butene-1, '»- diol and 3-Hydroxycycl ohe;: en.

The inventive method can be used with overprinting up to

Perform 703 kg / cm (10,000 psig) or more, preferably in the range from about 7 »O3 to 35 kg / cm overpressure (100 to 5000

psig), particularly in the range of about 21 to about 105 kg / cm gauge (300 to 1500 psig). The process can be carried out at temperatures from about 50 to about 200 ^° C., preferably from about 75 to 150 ^° C., and in particular from about 85 to about 130 ^° C.

The temperature and pressure can even be varied in a given reaction so that the efficiency of the hydroformylation or hydrogenation stages of the conversion from allylic alcohol to butanediol or substituted butanediol improved. For example, a special process can be carried out under the conditions of relatively low temperature and / or pressure and improve the selectivity of the hydroformylation reaction, and you can then (without isolation of the intermediate stages) under the conditions of higher temperature and / or Working pressure and improving the conversion of the hydroformylation starting materials to the desired diol products.

The ratio of hydrogen to carbon monoxide that is obtained according to the invention can vary widely. While having a molar ratio of hydrogen to carbon monoxide with a upper value of 10 or more and a lower value of 0.1

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or less, the preferred ratio is in the range of about 1 to about 5. In particular, the molar ratio is from hydrogen to carbon monoxide ranging from about 1.5 to about 3.

A solvent can advantageously be used in the process according to the invention use, especially one that is inert in terms of raw materials and products. One can also use reaction products use as a solvent. A large number of solvents such as aromatic and aliphatic can be used Hydrocarbons, esters, ethers, nitriles, alcohols, halogenated hydrocarbons, etc. including, for example Benzene, hexane, toluene, mesitylene, xylene, cyclohexane, ethyl acetate, methyl alcohol, methanol, n-propanol, tetrahydrofuran, Use chlorobenzene, methylene chloride, acetonitrile, etc., and their mixtures.

The process can be carried out batchwise or on a continuous or semi-continuous basis. Typical for a continuous or semi-continuous method is that the allylic alcohol is fed to a reaction vessel, by specifying the temperature and pressure conditions for the reaction has already made. The reaction vessel also contains the solvent and the catalyst. The diol products can be isolated from the catalyst by aqueous extraction or by distillation. You can use the catalyst in the reaction vessel in this pail in the non-aqueous Return the extraction phase or in the distillation residue. When the substrate used is allyl alcohol and a hydrocarbon solvent is used (especially an aliphatic hydrocarbon), one can remove the immiscible butanediol product from the solvent and the Isolate the catalyst by direct phase separation, whereby the addition of water is not necessary.

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The invention is explained in more detail below by means of examples.

Example I.

In a 300 ml autoclave from Autoclave Engineers Magnedrive were added 50.0 g of allyl alcohol (861 tnmol), 65 ml of benzene, 0.20 g of hexarhodiumhexadecacarbonyl (Rhg (CO) .. g, 0.188 mmol, 1.13 milliequivalents of Rh) and 0.92 g of tri-n-butylphosphine (4.52 mmoles). The mixture was put under pressure at 63 kg / cm (900 psi) with a mixture of H ₂ and CO (2: 1) and heated at 125 ^° C. for 1.5 hours, during which the gas mixture (2: 1) was added added a pressure of 42 to 63 kg / cm ² (600 to 900 psi) (332.5 kg / cm ² = 4750 psi total intake).

The mixture of the reaction product was subjected to a quantitative analysis by gas / Plüssig partition chromatography, with _n-pentanol being added as an internal standard. The presence of 31.6 g of 1,4-butanediol (41 $> yield), 7.3 g of 2-methyl-1,3-propanediol (9 ° yield), 19.7 g of n-propanol (33 ° β > Yield) and 4.1 g of isobutanol (6 % yield) was indicated. Their identity was proven by comparing the mass spectra and IR spectra of the products isolated by gas / liquid partition chromatography with those of pure samples (authentic)

Example II

The procedure was carried out as in Example I with the exception that 65 ml of hexane was used as the solvent. In 1.5 h at 125 ⁰ G were 290.5 kg / cm ² (4150 psi) with a pressure of 42 63 kg / cm ² (600 to 900 psi) a H _2/00-mixture (2: 1) recorded. The product mixture was a somewhat viscous two phase liquid. Analysis as above showed the presence of 31.9 g 1,4-butanediol (41 $> yield), 10.1 g 2-methyl-1,3-propanediol (13 "/> yield), 17.2 g n -propanol (33 i> yield) and 3.1 g of isobutanol (5% yield) of. Further, there was prepared a 1,4-butanediol-precursor 2-hydroxytetrahydrofuran called because of their mass spectrometry

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spectrum and IR spectrum determined (1.1 g, 1 # yield).

Example III

The autoclave was charged with 0.205 g of hexarhodium hexadecacarbonyl, 1.84 g of tri-ti-butylphosphine and 65 ml of benzene, then pressurized with 84 kg / cm ² (1200 psi) of a Hg / CO mixture (2: 1) and heated to 100 ^° C. After 15 minutes, the mixture was cooled and vented. Then 50.0 g of allyl alcohol were added and the vessel was again ^{pressurized to 84 kg / cm 2} (1200 psi) with the H ₂ / CO mixture (2: 1) and slowly heated to 70 ^° C. An exothermic reaction entered, which were regulated by cooling with water. A total of 234.5 kg / cm (3350 psi) of the gas mixture (2: 1) was taken up and at a pressure of 63 to

84 kg / cm (900 to 1200 psi) replenished within 30 minutes. the Analysis of the mixture at this point indicated the presence of 1,4-butanediol and 2-methyl-1,3-propanediol as the major products in addition to propanol, fropionaldehyde, isobutanol, isobutyraldehyde and the 1,4-butanediol precursor, 2-hydroxytetrahydrofuran.

The conversion was completed by repressurizing the vessel with 84 kg / cm ² (1200 psi) of the Hg / CO mixture (2: 1), ^{heating it at 125 °} C. for 1 hour, then cooling it and analyzing it. The products were 38.4 g 1,4-butanediol (50 $> yield), 17.7 g 2-methyl 1-1,3-propanediol (23 # yield), 5.0 g ii-propanol (10 Ί » Yield) and 7.1 g of isobutanol (11 $> yield). The total yield of diol precursors was about 1 %.

Example IV

The reagents described in Example I were added to the autoclave, with the exception that 6.7 g of tri-n-octylphosphine (18.1 mmol) were used instead of the tri-n-butylphosphine. The mixture was brought at 84 kg / cm (1200 psi) of H ₂ / CO Mix {(2: 1) into contact and heated to 85 ⁰ C. A total of 266 kg / cm ² (3800 psi) gas was within from 1.5 hours and supplemented at 63 to 84 kg / cm ² (900 to 1200 psi) and

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provided a mixture in which 1,4-butanediol and 2-methyl-1,3-propanediol were the main components of the hydroformylation products. Re-heating at 100 ⁰ C under a fresh Hp / CO mixture (2: 1) for an additional hour completed the conversion and generated a mixture comprising 35.6 g of 1,4-butanediol (46 ° / o yield), 5 , 3 g of 2-methyl-1,3-propanediol (7 "/ <> yield), 9.0 g of ri-propanol (17 " / <> yield) and 10.7 g of isobutanol (17 % yield). A small amount of a 1,4-butanediol precursor called 2-hydroxytetrahydrofuran (2 to 4 g, 3 to 5 / 1/2 yield) was also detected.

Example V

The general method of Example I was followed except that phenyl diethylphosphine (1.5 g, 9.0 mmol) was used as the modifying ligand. Within 30 min at 35 ^° C., a total amount of 157.5 kg / cm (2250 psi) with a pressure of 63 to 84 kg / cm ² (900 to 1200 psi) of the H ₂ / CO mixture (2: 1 ) and a mixture containing the diol precursors as major ingredients was produced. When heated to 125 ° C (63 to 34 kg / cm ² = 900 to 1200 psi) for 3 hours, the conversion to the diols was almost complete. Analysis of the products showed the presence of 38.7 g of 1,4-butanediol (50 $ yield), 15.6 g of 2-methyl-1,3-propanediol (20 % yield), 10.8 g of n-propanol ( 21 ° / o yield), 1.4 g of isobutanol (2 ° / o yield) and 5.0 g of 2-Hydroxytetrahydrof uranium as a precursor to 1,4-butanediol (7 $ yield).

Example VI

Was used and the reagents employed in Example I with the exception to the general method that 0.92 g of tri-n-butylphosphine (4.5 mmol) used, the reaction temperature kept at 85 to 100 ⁰ G, and the pressure in the Held in the range of 21 to 42 kg / cm ² (300 to 600 psi). In 1 hour under these conditions, a mixture of diols and diol precursors was produced in a ratio of about 2: 1. The temperature was increased to 125 ^° C. and the pressure to a range of

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56 to 84 kg / cm ² (800 to 1200 psi). After an additional hour under the latter conditions, the conversion to the diols was essentially complete. The analysis showed the presence in the product mixture of 31.1 g 1,4-butanediol (40 $> yield), 6.0 g 2-methyl-1,3-propanediol (8 $> yield), 14.3 g n_ -Propanol (28 # yield) and 6.8 g of isobutanol (11 % yield). The remaining 1,4-butanediol precursor (a mixture of 2-hydroxytetrahydrofuran and 4-hydroxybutyraldehyde) totaled about 2 g (2-6 yield).

Example VII

The general method of Example 1 was followed using 100 g of allyl alcohol, 0.40 g of Ilexarhodiumhexadecacarbonyl and 1.84 g of tri-n-butylphosphine (no addition of solvent) with the pressure at 42 to 63 kg / cm ² (600 to psi) with an H ₂ / C0 mixture (2: 1) and maintained the temperature at 90 ^° C. for 1 hour and at 125 ^° C. for a second hour. The products obtained in this case were 42.6 g 1,4-butanediol (27% yield), 6.6 g 2-Methy1-1,3-propanediol (4 ⁰ Jo yield), 38.1 g n_-propanol ( 37 5 ^ yield) and 15.1 g of isobutanol (12 # yield).

Example VIII

This example shows that you can use the diol product of the invention can be separated from the catalyst by aqueous extraction, and that mau return the catalyst directly to the reaction vessel can.

The method of Example I was initially followed. At the end of the reaction time, the product mixture was removed from the autoclave and extracted with 100 ml of water. The lower aqueous phase, which was somewhat emulsified, contained (according to the analysis with gas / liquid partition chromatography) 30.3 g of 1,4-butanediol (39% yield) and 4.9 g of 2-methyl-1,3-propanediol (6 i> yield).

The upper phase was led into the autoclave with 50.0 g of allyl

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alcohol back. After a second reaction cycle and the separation of the diol products, as described above, it was found that the aqueous phase had 26.5 g of 1,4-butanediol (34 °, Ό yield) and 13.9 g of 2-methyl-1,3 -propanediol (13 ^c , 6 yield).

Example IX

62.2 g of methallyl alcohol (861 mmol), 0.20 g of hexarhodiumhexadecacarbonyl (0.183 mmol, 1.13 milliequivalents of Rh), 0.80 g of triethylphosphine (63 fo) in isopropanol (0.53 g of triethylphosphine, 4th grade) were added to the autoclave , 5 mmol) and 65 ml of benzene, then pressurized to 34 kg / cm ² (1200 psi) with an H ₂ / CO mixture (2: 1) and heated to 100 C. In 3 h a total of 504 kg / cm (7200 psi) of gas absorbed and at 63 to 34 kg /

ο
cm (900 to 1200 psi) added. Analysis of the products showed the presence of 77.1 g of 2-methyl-1,4-butanediol (36 fi yield), 4.5 g of 2,2-dimethyl-1, 3-propanediol (5 Ά yield), 2, 5 g of 3-methyl-4-butyrolactone (3 ⁰ A yield), and 1.1 g of isobutanol (2 ^ yield). Their identity was proven by comparing the mass spectra and IR spectra of the isolated products with those of pure samples.

Example X

In the autoclave were added 62.2 g of crotyl alcohol (861 mmol), 0.202 g of hexarhodiumhexadecacarbonyl (0.138 mmol, 1.13 milliequivalents Hh ^ 1.34 g of tri-n-butylphosphine (9.09 mmol) and 65 ml of benzene was heated under a supplemented pressure of £ 3-84 kg / cm (900 to 1200 psi) of H ₂ / C0 Hischung (2: 1). / 1 h 100 ⁰ G and 2 h at 125 ⁰ C analysis of the Product mixture showed the presence of 43.0 g of 2-ethyl-1,3-propanediol (48 "/> yield), 22.3 g of 2-methyl-1,4-butanediol (25% yield), 7.1 g of 2 methyl-1-butanol (9 $ yield), 2.0 g ri-butanol (3% yield), 0.4 g of i-amyl alcohol (0.5 ⁰ A yield) and 0.2 g of 1, 5-pentanediol (0.2 <f _a yield).

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Example XI

Based on the results from Examples I to X it can be seen that when using cinnamon alcohol as a substrate in the In carrying out the invention, the products contain 2-phenyl-1,4-butanediol, 2-benzyl-1,3-propanediol and 3-phenyl-1-butanol.

Example XII

Based on the results from Examples I to X, it can be seen that when 2-butene-1,4-diol is used as substrate in carrying out the invention contain the products 2-hydroxymethyl-1,4-butanediol and 2-methyl-1,4-butanediol.

Example XIII

Based on the results from Examples I to X, it can be seen that when 3-hydroxycyclohexene is used as the substrate in the practice of the invention contain the products 3- (hydroxymethyl) cyclohexanol and 2- (hydroxymethyl) cyclohexanol.

Comparative example

This example shows the unusual tendency of allylic alcohols to undergo conversion to alcoholic ones (Diolic) hydroformylation / hydrogenation products among the subject to conditions according to the invention by using allyl alcohol and allyl acetate as substrates for the working method compares. The applicability of the method described in US Pat. No. 3,239,566 (Slaugh and Mullineaux) to allyl acetate distinguishes this method from the invention.

In the autoclave were added 36.3 g of allyl acetate (861 mmoles), 0.21 g of hexarhodium hexadecacarbonyl (0.197 mmoles, 1.13 milliequivalents of Rh), 0.77 g of tri-ii-butylphosphine (3.8 mmoles) and 65 ml of benzene , pressurized to 63 kg / cm ² (900 psi) with a Hg / OO mixture (2: 1) and was heated to 125 ^° C. within 2 h

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a total of 444.5 kg / cm (6350 psi) of the gas mixture (2: 1) was taken and supplemented at 42 to 63 kg / cm (600 to 900 psi). Analysis of the products showed the presence of 36 '; Acetic acid (70 ft. Yield), 30.0 g. 4-acetoxybutyraldehyde (27 ft. Yield), 23.4 g. N. -butyraldehyde (3B ft. Yield), and 19.9 g. Isobutyraldehyde (32 ft. Yield). No hydroformylation / hydrogenation product, 4-acetoxybutanol, was detected.

When the method above was carried out with 50.0 g of allyl alcohol in place of the allyl acetate, the products were 29.6 g of 1,4-butanediol (33 # yield), 6.0 g of 2-methyl-1,3-propanediol (B. $ Yield), 22.2 g ri-propanol (43 ft yield) and 4> 7 g isobutanol (7 % yield).

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Claims (11)

Claims Vi i. Process for the preparation of butanediol or substituted Butanediols, characterized in that an allylic alcohol, carbon monoxide and hydrogen are present in the presence brings a rhodium carbonyl catalyst into contact, incorporating a triorganophosphorus modifier, that by one of the formulas below is pictured: I. II. R ₁ -PR ^ -PR ₁ III. R ₁ -PR) ₁ -PR ₁ \ ^4/1 wherein R ₁ , R ₂ ^{and R} 3 are independently selected from the group consisting of ^G 1-2CT ^alkyl ~ * ^c i_20 "" ^alkoxy "^{> C} 3-20 ~ ^cycloalkyl ~» ^C 6-20 "" ^aryloxy ~ »Gg_ ₂ Q-aryl- , C ^ _ ₂₀ alkaryl and C ₇ _ ₂₀ aralkyl radicals and their Mixtures formed group and the radicals R ^ independently from the group formed from C-OQ-alkylene, C ^ _-2 Q-cycloalkylene, Cg_ ₂₀ -arylene, G ^ _ ₂₀ -alkarylene and C ^ _ ₂₀ -aralkylene radicals with the proviso that at least 809828/0687 ORIGINAL INSPECTED 4555-3CH-25O? one of the radicals i: (^ ₁ , R ₂ , R ₃ or R ₄ ) is an alkyl, cycloalkyl, alkylene or cycloalkylene radical. 2. The method according to claim 1, characterized in that ditß the allylic alcohol is made from the allyl alcohol, methallyl alcohol, Crotyl alcohol, cinnamon alcohol, 2-butene-1,4-diol and 3-hydroxycyclohexene formed group. 3. The method according to claim 1 or 2, characterized in that that one uses allylic alcohol as the allylic alcohol. 4 ·. Method according to one of the preceding claims, characterized characterized in that methallyl alcohol is used as the allylic alcohol. 5. The method according to any one of the preceding claims, characterized in that the triorganophosphorus modifying agent from the one from tri-n-butylphosphine, tri-n-octylphosphine, Triethylphosphine and Phenyldläthylphosphin formed group selects. 6. The method according to any one of the preceding claims, characterized in that there is a ratio of phosphorus in Triorganophosphorus mod if izierungsmittel for rhodium in the hydride carbonyl in the range of about 2 to about 16 applies. 7. The method according to any one of the preceding claims, characterized in that the method is carried out at an overpressure from e performs. pressure from about 7 to about 350 kg / cm (100 to 5000 psig) S. A method according to any one of the preceding claims, characterized in that one carries out the process at a temperature of about 50 to about 200 G ^0. 9. The method according to any one of the preceding claims, characterized in that the process is carried out in the presence Ainet does not perform miscible solvent with water. 809828/0687 10. The method according to claim 9, characterized in that; j the butanediol or the substituted butanediol products of the catalytic converter and the solvent that cannot be picked up with water separated by aqueous extraction. 11. The method according to any one of the preceding claims Production of 1,4-butanediol, characterized in that one (a) Allyl alcohol, carbon monoxide and hydrogen in the presence of a hydrocarbon solvent and a rhodium carbonyl catalyst brought into contact with each other, incorporating a triorganophosphorus-iodine izierungsmittel, which is represented by one of the following ports: I. K ₁ -PH, ¹ I J II. III. R., - PR - PB ₁ wherein one R _1, Rp and R ^ are independently selected from the group consisting of C _1-20 alkyl, C _1-20 -AIkOXy-, C _3-20 -CyClOaIlCyI-, C ₆ _ ₂₀ aryloxy, aryl-CgoQ , C " ₂₀ -alkaryl and u ₇ _ ₂₀ -aralkyl radicals and their mixtures formed group and the radicals R. independently from one another from the group consisting of C ₁ ", .- alkylene-, J _x , ^ - cycloalkylene-, ι— to 3-tLKj residues Cg_ ₂₀ arylene, C ₇ _ ₂₀ -Alkarylen- and C _"20 -aralkylene / group formed under the condition selects that at least one of the radicals R is an alkyl, cycloalkyl, alkylene or cycloalkylene, and (b) that one under substantially anhydrous conditions Ln a solvent phase of a hydrocarbon which the Contains catalyst, and separates a second phase which contains a substantial amount of 1,4-butanediol. 809828/0687