DE2023831A1 - Process for the production of mercaptans - Google Patents

Description

LAWYERS

DR. JUR. DIPL-CHEM. WALTER BEIL

ALFRED HOEPPENER U. May 1970

DR. JUR. DIPL-CHEM. H.-J. WOLFF

DR. JUR. HANS CHR. BEIL '/

FRANKFURT AM MA1N-HOCH3T AOELOHSTRASSt Se

Our no.16 259

Stauffer Chemical Company New York IWfflX & ms & m » New York / V.St.A.

Process for the production of mercaptans

The invention relates to a process for the production of mercaptans, which is characterized in that one hydrogen sulfide with a compound consisting essentially of hydrocarbons having an olefin linkage in the presence of a free radical initiator and an amount acting as a promoter. an organic compound of trivalent phosphorus of the general formula

R '(X) _a

in which X, Y and Z each represent a chalcogen with an atomic weight between 15 and 33 »a, b and c each represent 0 or and R ¹ , R ″ and R ″ ¹ denote hydrocarbon radicals with 1 to 20 carbon atoms.

009848/1958

* m O em

The reaction of hydrogen sulfide with hydrocarbons having an olefin bond is known. However, the process is generally characterized by incomplete conversion and low yields Mercaptans off. Although the reaction of hydrogen sulfide initiated by free radicals

O (r01efinen "directly to usable primary mercaptans leads to the low yields and the formation of by-products such as sulfides and disulfides Induced manufacturers to take the route of indirect syntheses and primary mercaptans, for example synthesize from chlorinated hydrocarbons.

To increase the yields of the desired mercaptans, various catalysts were used in the free Radical triggered implementation used. Free radical initiators such as organic azo compounds, Organic peroxides and organic percarbonates have been used as such or in conjunction with various Promoters like water and nickel are used to increase olefin conversion and to increase mercaptan yield increase. However, such catalysts require high temperatures and large amounts of catalyst, wherein however, a large amount of olefin remains with no conversion.

For the addition of hydrogen sulfide to an olefin actinic light was also used. However, this makes this procedure a costly, difficult to achieve and maintenance equipment is necessary, and the olefin conversions are still comparatively low compared to the results of the present process. To the Degree of conversion in the photolytic conversion to increase were different promoters like water and

009848/1953

organic sulfide was used, but quantitative conversion was not achieved here either. Trialkyl phosphites have been used as promoters in conjunction with actinic light, but the ratio of mercaptan to sulfide decreases with increasing olefin conversion using progressively longer exposure times. Even though? ⁴ , so the olefin conversion is increased, the mercaptan yields still remain relatively low. In addition, in the procedure according to the invention, the implementation times are much shorter and the cat-

this ύ

lysator quantities much lower than / in the case of photolytic ^

Method is the case.

It has been found that quantitative olefin conversions and greatly increased mercaptan yields can then be achieved when the reaction of hydrogen sulfide with a compound consisting essentially of hydrocarbons with at least one olefin bond in the presence of a free radical initiator and one Promoter is carried out in the form of an organic compound of trivalent phosphorus.

The mercaptans in the present invention find obtained largely similar immediate uses as raw materials for the preparation of insecticidal, herbicides, repellents (repellents), rubber vulcanizing agents and surfactants.

The invention relates to free radical initiated Hydrogen sulfide conversions in contrast to through Acid or base catalyzed reactions. In the reaction catalyzed by ions (acid or base) the hydrogen sulfide deposition takes place over

009848 / 19E8

the olefin linkage according to Markovnikov's rule, i. a "normal" addition takes place in which the sulfhydryl group attaches to the unsaturated carbon atom with the lower number of hydrogen atoms attached to it. When initiated by free radicals Implementation leads to an "abnormal" or an addition which goes against the Markovnikov rule, i.e. the sulfhydryl group settles on the unsaturated carbon atom with the greatest number of hydrogen attached to it atoms at. For example, an OC olefin is under Reacted acid-catalyzed conditions, a secondary mercaptan is formed, namely 2-thiol; however will in the conversion initiated by free radicals, the δ6-01efin into a primary mercaptan, i.e. into 1-thiol convicted.

According to the invention, the reactions of hydrogen sulfide initiated by free radicals are carried out with an im Compound consisting essentially of hydrocarbons and having an olefin bond in the presence of a free one Free radical initiator.

According to the invention, hydrogen sulfide and a substituted or unsubstituted hydrocarbon compound are used with at least one olefin bond in the presence of a free radical initiator and implemented an organic compound of trivalent phosphorus. The reaction can be carried out with or without a diluent take place. Organic compounds of trivalent phosphorus, which in this implementation as Promoters work have the general formula

009848/1958

R ¹ (X)

2023S31

- 5 - ■■■■ / ^■:

(Y) _b R "

a \

^ (Z) ₀ R ^1I!

in which X, Y and Z are chalcogens with an atomic weight between 14 and 33, a, b and c each denote Ö or 1 and R ¹ , R ″ and R ¹¹ 'denote hydrocarbon radicals with 1 to 20 carbon atoms According to the preferred embodiment of the invention, these radicals can be lower alkyl radicals with 1 to H carbon atoms or aryl radicals with 6 to 8 carbon atoms. Examples of such compounds are the alkyl - and arylphosphines? -phosphites, -phosphonites and -phosphinites such as trimethylphosphine, tributylphosphine, triphenylphosphine, trimethylphosphine, tributylphosphite, trihexylphosphite, tritolylphosphite, trimethylphosphonite, triphenylphosphonite, further examples of such compounds are tributylphosphinites, the triphenylphosphinites, the triphenylphosphonite, the triphenylphosphonite, the compounds of such phosphinophosphonite, the triphenylphosphonite, the compounds of these phosphinophosphinites, the triphenylphosphinite, triphenylphosphonite, tributylphosphinite, triphenylphosphonite, triphenylphosphinite, triphenylphosphinite, tributylphosphine, triphenylphosphonite, examples of such , Phosphonites and phosphinites such as triphenyl thiophosphite,

Trimethyl thiophosphite, trimethyl thiophosphonite, tri- λ

phenyl-thiophosphinite and tributyl-1-thiophosphite.

Preferred promoters of this reaction are the trimethyl, triethyl, ^{LRIP 'ro} Py ^1' 'and tributyl Tripheny! Phosphites and phosphines.

Free radical-forming which can be used according to the invention Initiators include peroxide compounds / j organic Azo compounds, peracids and percarbonates. The various azo initiators can therefore be used, which cause the addition of hydrogen sulfide to an olefin via free radicals Bring about mechanism. According to the invention, for example, the azo initiators can be used

009848/1958

where an acyclic azo group -N = N is bonded to various types of non-aromatics, ie to aliphatic or cycloaliphatic carbon atoms, at least one of which is tertiary. These azo compounds are described in US Pat. No. 2,551,813. Examples of these are azo-bis-isobutyronitrile, azo-bis- ( CC » ^ -dimethylvaleronitrile), azo-bis- (QC-methyl-Cfcf-carboxybutyronitrile) , Azo-bis (isobutyramidine hydrochloride), azo-bicyclohexane-carbonitrile, Q £ - (carbamyl-azo) -isobutyronitrile, oC- (carbamyl-azo) - Οζ ^ -dimethylcaleramide, hexyl- Qd- (carbamyl-azo) - αςJ ^ -dimethylvalerate, Qi, OC ¹ -azo-bis- (OT-methylene-anthonitrile), oc. ₉ o <: - Azobis - ((X-ethylbutyronitrile), Qc , OC- azo-bis- (c £ - cyclopropyl-propionitrile), OiT, OC-azo-bis- ( CX ₃ ST'-dimethylcapronitrile) and!, l'-Azo-bicycloheptane-carbonitrile). Preferred azo compounds are azo-bis-isobutyronitrile and azo-bis- (O ^ fr -dimethylealeronitrile). Although di-tert-alkyl peroxides such as di-tert-butyl peroxide are highly effective initiators for the process according to the invention, the other diacyl peroxides, alkyl hydroperoxides, alkyl peroxyesters and diacyl peroxides can also be used as effective initiators for this process. Peroxide compounds which can be used according to the invention are, for example, di-tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, pinane hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-methane hydroperoxide, p- Chlorobenzoyl peroxide, 2,! »- dichlorobenzoyperoxide, hydroxy-heptal-dehydroperoxide, dibenzal-diperoxide, methylisobutyl-ketone-peroxide and cyclohexanone-peroxide. Preferred peroxide compounds are di-tert-butyl peroxide and tert-butyl hydroperoxide. The "hot catalysts" such as percarbonates, per-

009848/1958

acids and peracid esters can be used according to the invention. The term "hot catalysts" denotes those whose half-life at a temperature below 60 ^° C. is ten hours.

Examples of percarbonates are isopropyl percarbonate, Diisopropyl peroxydicarbonate and t-butyl peroxyisopropyl percarbonate; Examples of peracids and peracid esters are t-butyl perbenzoate, t-butyl peroxypivalate, Di-tert-butyl-diperphthalate, t-butylpermaleic acid, t-butyl peracetate, t-butyl peroxyisobutyrate and t-butyl perphthalic acid.

The initiators to be used according to the invention have hitherto been used at temperatures which were high enough to decompose the initiator into free radicals, but at the same time were also low enough to control the half-life of the initiator so that this decomposition was about 1 up to about 6 hours. The optimal temperature changes with the respective initiator and pressure. So far, azo-bis-isobutyronitrile (AIBN) for the addition of hydrogen sulfide to olefin thus at temperatures of about 80 to about Uo ⁰ C. Di-tert .butylperoxid was used at 130 to 16O ⁰ C, tert-butyl hydroperoxide at about 120 to about 150 ⁰ C. However, according to the inventive method lower temperatures can be used, without that olefin and Mercaptanausbeute substantially affected. So azobisisobutyronitrile can at about 40 to about 110 ^° C. can be used without significantly impairing the yield; this is even b at a temperature of

009848/1958

only 20 ⁰ C still effective. In contrast, without the present promoters, the minimum temperature for azo-bis-isobutyronitrile under the same pressure was about 70 ^° C. The temperature at which the initiator can be used according to the procedure according to the invention changes depending on the initiator and pressure used, but can each initiator can be used at a lower temperature than was previously possible without a promoter according to the invention. The normal reaction temperatures are between about 30 and about 200 ⁰ C, the area according to the invention preferred liegtjzwischen about 60 to about 130 ⁰ C. A further advantage of the inventive method lies in the fact that one can operate with considerably reduced amounts of initiator, without being affected that olefin or Mercaptanausbeute will. This is demonstrated in the later examples.

Although water can be present in the system, better yields are obtained if the reaction is anhydrous. In order to increase the formation of mercaptans as much as possible and to keep the formation of thioesters as low as possible, the ratio of hydrogen sulfide to hydrocarbon should be at least 1 or more, ie about 1 to about 20 moles of H ₂ S per mole of hydrocarbon should be used . The higher this molar ratio, the greater the molar ratio of mercaptan to sulfide in the product.

In the process according to the invention, a compound consisting essentially of hydrocarbons with at least an olefin bond is used. The term "consisting essentially of hydrocarbons" means that the compound consists essentially of hydrogen and carbon. The designation closes Hydrocarbons with substituents that represent the basic

009848 / 19B8

Do not affect the character of the procedure. The hydrocarbon can have two or more olefin linkages exhibit; e.g. 1,3-butadiene, isoprene, 1,5-hexadiene, 1,7-octadiene or vinyl yelohexene be used. However, the hydrocarbon must have at least one olefin bond in the aliphatic or In contrast to the unsaturated bond, cycloaliphatic grappa contain in an aromatic molecule like benzene. An alkyl, cycloalkyl, aryl,

Arylalkyl, alkaryl or another branched or Λ

straight-chain hydrocarbon substituent bound '. <'. ■ be. Furthermore, the groups bonded to the olefin carbon atoms can be substituted hydrocarbons, the substituents of which are inert towards the reaction according to the invention. Examples of such substituents are: cyano, carboxyl, carbonyl, tertiary amines, halogens, sulfoxides, sulfones, hydroxyl, ethers, thioethers, carboxylic acid esters or amides. Trivalent and pentavalent phosphorus compounds can also be bound to the hydrocarbon. The invention is particularly suitable for the production of primary mercaptans from hydrocarbons having an olefin bond to a terminal carbon atom, for example an O6 olefin. "

For example, 1-butene can be converted into 1-r-butanethiol with high yields. Likewise, 1-octene and 1-dodeoene can be converted into l-octanthiol and 1-dodecanethiol, respectively. Thus (XrOletins with 2 to 30 carbon atoms can be converted into their corresponding primary mercaptans. Olefins suitable for this reaction include ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 1- Octene, 1-nonene, styrene, 1-dodecene,

0098A8 / 1958

- ίο -

1-decene, 1-tridecene, 1-undecene, 1-heptadecene, 2-methylhexene-1, 3-methyl-2-ethyl-1-pentene, 3 _S 3-dimethyl-1-heptene, M-methyl-1-propyl -l-pentene-vinyl-cyclohexane, 3-phenyl-l-pentene, l _s 3-butadiene, 1,3-pentadiene, 1,5-hexadiene, 1,6-octadiene, 3,4-diethyl-l, 5-hexadiene, propylene dimer, propylene trimer, propylene tetramer _s 3-chloro-l-hexene, 5-nitro-l-pentene, p-chlorostyrene, m-nitrostyrene and 5-cyano-l-pentene »

In addition to the olefins described above, according to the invention those olefins are also used which are directly bonded to the olefin carbon atoms, have inert groups compared to the present implementation. Examples of such inert groups are: Cyano, halogen, ether, carboxyl and carboxylate (including both the acrylic acid esters where the olefin carbon atom to the carboxyl carbon atom is bonded, as well as the vinyl ester, in which the olefin carbon atom to an Oxygenstom of Carboxyl group is bonded) and the like. Examples of such compounds are vinyl chloride, vinyl bromide, 3-ethoxy-pentene-2, 2-chloro-eicosen-2, 2-butenylphenyl-ethyl ether, Methy1-vinylather, divinylather, Acrylic acid, ethyl acrylate, methyl methacrylate, maleic acid or 2-cyano-2-butene.

The reaction can be carried out batchwise, continuously or in a series of reactors. For example, hydrogen sulfide, olefin, initiator and promoter can be introduced all at once, or olefin and hydrogen sulfide introduced as separate streams into a continuous reactor system are, the initiator and promoter in the desired proportions either separately or together with

009848/1958

- ii -

properly fed to the olefin or hydrogen sulfide. Optionally, a serpentine reactor can also be used, with the initiator being injected at various points along the serpentine tube. According to a further embodiment of the invention, the trivalent phosphorus promoters can be prepared in situ by adding phosphine to the olefin to form the organic compounds of the trivalent phosphorus, which can then act as promoters. G

The amount of the organic to be used in the present invention Phosphorus promoters varies within wide limits and is of different factors such as the respective promoter itself, the amount of initiator and temperature dependent. The phosphorus compound is to be used in such an amount that the reaction promoted and the conversion of the unsaturated compound is increased without a substantial one Implementation with the resulting mercaptan takes place. For most uses, the amount of promoter is preferably 0.001 to 1.0 mole per mole of olefin linkage. At concentrations of more than 1.0 mol - (|

mercaptan formation decreases considerably as a result of the reaction between promoter and product. The amount of initiator can be changed and depends on the type of initiator itself and the amount of promoter used and the reaction temperature used. For most normal purposes, the amount of initiator will be in the range preferably between about 0.0001 and about 0.25 moles per mole of olefin linkage.

009848/1958

The inventive reaction can with or without Can be carried out using a diluent. The diluent should be opposite each other behave inertly to the reactants and the products. Suitable diluents include saturated and aromatic hydrocarbons such as pentane, hexane, octane, cyclohexane, benzene, toluene and Xylene.

The following examples serve to explain the Invention.

The experiments were carried out in such a way that the catalyst and, if a solvent was used, 50 ecm of such an inert solvent such as benzene or hexane in a stainless steel autoclave Brought in steel, which with a gas inlet opening,

ρ a thermocouple, one designed for 210 kg / cm

ο was equipped with a pressure gauge and a tear disk measured at 140 kg / cm. A glass shim was often used for the sake of simplicity, but it has been demonstrated that the implementation takes place without this shim. The autoclave was then closed and evacuated, but it was found that evacuation is not necessary. After cooling the autoclave in a nitrogen bath, olefin and hydrogen sulfide were introduced. The autoclave was then heated within 1 to 3 hours and kept at the reaction temperature for a certain time. The in-ethylene experiments was developed at 90 to 100 ⁰ X maximum pressure

009848/1958

'3

84 kg / cm. The propylene conversions usually reached a maximum pressure of 56 kg / cm. The pressures decreased as the number of carbon atoms in the olefin increased. In Table I the results are compiled which were mixed with 0.1 g azo-bis-isobutyronitrile (AIBN) as initiator in 50 cc of solvent (benzene) at temperatures between 90 and 100 ⁰ C achieved. Example No. 1 was carried out as a control experiment without the use of a promoter.

TABEL

Example no. X 2 -3 ¹ 4. 0.2 eg · ' t ¹ 8th 0.2 Feed (mole) ! 1.0 Ethylene 0.2 0.2 0.2 .1· Propylene 0.2 1.0 0.2 Dodecene-1 0.2 Octene-1 H ₂ S 1.0 t, o 1.0 1.0 i, c i, c 2.0 Promoter (g) Triphenylphosphire 2.0 2.0 72 Triphenyl phosphite 2.0 2, C 2, C Tributylphosphine 2.0 84 91
■ Trimethyl phosphite Mercaptan 100 prey (SS) 22nd 74 67 71 76 70 Olefinic wall lung {%) 36, 100 97 92 IOC 87

00 9 8 48/1958

The above data reveal the increased product yield due to the phosphorus compounds used as promoters is achieved.

Experimental examples 9-11 were carried out using peroxide initiators instead of AIBN, the corresponding Results are shown in Table II. The temperatures were different depending on the one used Peroxide changed but were in the range of 110

ο ^Ώ
up to 140 ° C. The control experiment of Example 9 was carried out without the use of a promoter.

TABEL

II

Example no. 9 10 11 Feed (mole) Ethylene 0.2 0.2 0.2 H ₂ S 1.0 1.0 1.0 Peroxide (g) ditert.Butyl peroxide 0.5 0.5 tert-buty! hydroperoxide 0.5 Promoter (g) trimethylphosphite 2.0 Triphenyl phosphite 2.0 Mercaptan yield ( %) 31 94 92 Olefin Conversion (%) 70 100 100

From these data it can be seen that the promoter also proves to be very effective _{in the H 2 S addition * to olefin initiated by peroxide.} The promoter effect

009848/1 958

of these compounds is also evident in the reaction initiated by peracid and percarbonate. the Temperature ranges change depending on the initiator used.

Experimental examples 12-18 were carried out with different amounts of initiator and promoter. AIBN was used as the initiator and trimethyl phosphite (TMP) as the promoter. The charge contained 0.1 mole of ethylene and 1.0 mole of hydrogen sulfide in 50 cc of inert solvent, in this case benzene. The temperatures were about 85 to 95 ^° C., the reaction times about 6 hours.

TABLE III

example
No. .12 13th 14th 15th 16 17th 18th 19th 20th AIBN (g) 0.1 0.01 0.01 0.01 0.01 0.01 0.03 0.04 0.01 TMP (g) 2.0 2.0 2.0 1.0 0.75 0.5 0.5 0.5 Mercaptane
yield
(*) 96 84 75 84 74 61 69 70 Olefin
umwand-
lung (*) 100 100 100 100 100 81 94 100 8th

As can be seen from Examples 12-14, can when using a promoter according to the invention, the amount of initiator is considerable, in this case by ten times, be reduced, but still dne complete Olefin conversion is retained and the mercaptan yield is subject to only a slight decrease. Examples 15 and 16 make it clear that in the

009848 / 1-958

low initiator amount, the amount of promoter can be reduced by half, the complete conversion still being retained and good yields being achieved. In contrast, Example 17 shows that when the amount of promoter is reduced to below 1.0 g / 0.2 mol of ethylene, the promoter action begins to decrease, resulting in lower ethylene conversions and lower mercaptan yields. Examples 18 and 19 show that even with the same amounts of promoter, quantitative conversion can be achieved by a very slight increase in the amount of initiator used. However, even at this low level of promoter, the promoter discrepancy is still quite clear. Using 0.01 g of AIBN in the absence of the promoter, as was the case in Example 20, the olefin conversion reached less than 10 % _t and an insignificant yield of the desired mercaptan was obtained. It can therefore be concluded from these data that the promoters according to the invention not only bring about an increase in the olefin conversion and the mercaptan yield, but, contrary to expectations, also enable the amount of initiator to be greatly reduced.

The test examples 21-23 were at different Temperatures carried out. The control experiment of Example 21 was carried out without a promoter, Examples 22-23 were run using 1.0 g TMP, 0.01 g AIBN, 0.2 mole ethylene and 1 mole Hydrogen sulfide in 50 ecm benzene. The results are shown in Table IV. The experimental examples 24 - 25 were using 0.01 g AIBN, 1.0 g of trimethyl phosphite, 0.2 mol of ethylene and 1 mol Hydrogen sulfide carried out, the reaction time was changed. Examples 26-27 were carried out under the same conditions as Experiments 2 ^ -25

009848/1958

- 17 -

carried out, but the olefin used was propylene Table IV also contains the results of these experimental examples.

TABEL

IV

example
No. 21 ⁺⁺ 22nd 23 24 25th 26th 27 Time
(Hours) 6th 5 6th 3 1 4th 1 Temperate. (° CO 60 60.1 50-4 80-90 86 85-90 90 Mercaptane
yield no 80 78 70 80 78 71 Olefin
umwand-
lung no 100 100 100 100 100 100

++ 3

without a promoter.

As examples 21-23 prove, when used of the promoters according to the invention, the initiators are used at lower temperatures than in the absence the former. From the experimental examples 24-27 it can be seen that the present process even with Reaction times of just one hour lead to quantitative conversions and high yields.

Further experimental examples (28-30) were used extremely short response times. These reactions proceeded at a temperature of

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95 C using a hydrogen sulfide / ethylene molar ratio of 5: 1 and using *> n 0.008 mol TMP and 0.00006 mol AIBN / 0.2 mol ethylene. Table V contains the results of these tests.

TABEL

Example no. 28 29 30th Heating time (min.) 10 9 12th Response time (min.) 20th 15th 10 Mercaptan yield (%) 62 68 62 Olefinura Conversion (%) 94 100 100

The experimental examples 28-30 show that also with a considerable shortening of the reaction times still quantitative olefin conversions with only slight ones Reduction of the mercaptan yield can be achieved. According to the invention, the reaction times can be reduced by ten times compared to the previously known, while still quantitative Conversions and higher mercaptan yields can be achieved.

Examples 31 and 32 were carried out without the use of a diluent. Both experiments were carried out for about one hour at 90 ^° C. using 1 mol of hydrogen sulfide. The results achieved here are summarized in Table VI.

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TABLE VI

Example no. (X) 31 32 AIBN (g) (X) 0.01 0.01 TMP (g) 1.0 1.0 Propylene (mole) 0.2 Ethylene (mole) 0.2 Mercaptan yield 84 71 Olefin conversion 100 100

Experimental Examples 31 and 32 show that the inventive Reaction with or without a diluent to achieve essentially quantitative olefin yields can be carried out; however, the use of diluents is usually achieved somewhat higher mercaptan yields.

As all the preceding examples demonstrate, one achieves with implementation carried out according to the invention Surprisingly high mercaptan yields with a simultaneous reduction in the amount of initiator and the reaction time and the reaction temperature.

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Claims (23)

Claims Process for the preparation of mercaptans, characterized in that one uses hydrogen sulfide with an olefin-bonded compound consisting essentially of hydrocarbons in the presence a free radical initiator and acting as a promoter amount of an organic compound of trivalent phosphorus of the general formula R. (X) _a __P ^ (Z) R ^'11 in which X, Y and Z each denote a chalcogen with an atomic weight between 15 and 33 » a» b and c each denote 0 or 1 and R ¹ , R ″ and R ¹¹¹ denote hydrocarbon radicals with 1 to 20 carbon atoms. 2. The method according to claim I _9, characterized in that the compound of trivalent phosphorus is used in an amount of about 0.001 to about 1.0 mol per mole of hydrocarbon compound. 3. The method according to claim 1, characterized in that the reaction is carried out in an inert diluent. 4. The method according to claim 1, characterized in that one is essentially composed of hydrocarbons 00984 8- / 1958 existing compound <J £ -olefin with 2 to about 30 carbon atoms used. 5. The method according to claim i, characterized in that there is a free radical-forming initiator Azo initiator used. 6. The method according to claim 1, characterized in that that a peroxide initiator is used as the initiator which forms free radicals. 7. The method according to claim 1, characterized in that one as free © forming radicals! An initiator Percarbonate initiator used. 8. The method according to claim 1, characterized in that the initiator which forms free radicals is used Peracids or their esters are used. 9. The method according to claim 1, characterized in that that as a compound consisting essentially of hydrocarbons, ethylene, propylene,! -butene, 1,3-butadiene, 1,5-hexadiene, 1-octene, 1-dodecene, Tetrapropylene, styrene or vinyl chloride are used. 10. The method according to claim 1, characterized in that the organic phosphorus compound is a · Trialkyl phosphite used. 11. The method according to claim 10, characterized in that the organic phosphorus compound is trimethyl phosphite or triethyl phosphite is used. . 009848/1958 12. The method according to claim 1, characterized in that that a trialkylphosphine is used as the organic phosphorus compound. 13. The method according to claim 12, characterized in that the organic phosphorus compound is tributylphosphine used. 14. The method according to claim 1, characterized in that one is used as the organic phosphorus compound Triaryl phosphite is used. 15. The method according to claim 14, characterized in that the organic phosphorus compound is triphenyl phosphite used. 16. · The method according to claim 1, characterized in that the organic phosphorus compound is a Triarylphosphine used. 17. The method according to claim 16, characterized in that the organic phosphorus compound is triphenylphosphine used. 18. The method according to claim 5, characterized in that the azo initiator is azo-bis-isobutyronitrile or azo-bis (dimethylvaleronitrile) is used. 19. The method according to claim 6, characterized in that a hydroperoxide is used as the peroxide. 009848/1958 20. The method according to claim 19 »characterized in that that tert-butyl hydroperoxide is used as the peroxide. 21. The method according to claim 6, characterized in that the peroxide used is benzoyl peroxide or di-tert-butyl peroxide used. 22. The method according to claim 7 »characterized in that that isopropyl percarbonate is used as the percarbonate. 23. The method according to claim 8, characterized in that that tert-butyl peracetate is used as the peracid. For Stauffer Chemical Company Lawyer 009848/1958