PL150429B1 - - Google Patents

Description

The present invention relates to a process for the hydroformylation of an ethylenically unsaturated organic compound with carbon monoxide and hydrogen. Carbonylation reactions are known to be assisted by the use of modified Group VIII metal catalysts, such as those containing a Group VIII transition metal complex - phosphorus ligand. Carbonylation processes to produce products oxidized in the presence of a catalyst generally involve reactions of an organic compound with carbon monoxide and, preferably, still another reactant, in particular hydrogen. They are known, see e.g. J. Falbe, "New Synthesis With Carbon Monoxide", Springer Verlag, New York, 1980. These processes include the carbonylation of organic compounds such as olefins, acetylenes, alcohols and active chlorides with carbon monoxide or carbon monoxide alone, either with hydrogen, alcohol, amine or water, and ring-closure of functional unsaturated compounds such as amides with CO. One of the main types of known carbonylation reactions is the production of oxidized products such as aldehydes by hydroformylation of an olefinic compound with carbon monoxide and hydrogen in the presence of a Group VIII transition metal-phosphorus ligand complex in which the phosphorus ligand is triorganophosphine or triorganophosphite, possibly followed by an aldolization reaction. It is known that the phosphorus ligand used in the catalyzed carbonylation process can directly influence the result of this type of process. The choice of the phosphorus ligand to be used in the transition metal catalyzed carbonylation process depends largely on the intended end result and obtaining the best overall processing efficiency may require a compromise from a number of factors as it is known that not all phosphorus ligands give the same results when it comes to o all factors and e2 150 429 all conditions. And so e.g. In the case of hydroformylation, factors such as product selectivity, catalyst reactivity and stability, and ligand stability are often essential in selecting the phosphorus ligand. In addition, such selection may also depend on the type of olefinic starting material used in the hydroformylation reaction since not all olefins have the same level of reactivity under all conditions. And so e.g. , intrinsic olefins, and hindered α-olefins such as isobutylene are generally much less active than hindered α-olefins. Also, especially the product, process and / or catalyst yield results can be obtained by using a special catalyst or by using a special metal-phosphorus ligand catalyst. And so e.g. , US Pat. No. 3,527,809 describes how α-olefins can be selectively hydroformylated using rhodium-triorganophosphine ligand or triorganophosphite complexes to give oxidized products with a high content of normal aldehydes. In contrast, US Pat. Nos. 4,148,830 and 4,247,486 disclose the same results for recycle operations for both liquid and gas using a rhodium-triphenylphosphine ligand catalyst. U.S. Patent No. 4,283,562 discloses that in a rhodium-catalyzed hydroformylation process for olefins to produce aldehydes, branched chain alkylphenylphosphine ligands or branched-chain cycloalkylphenylphosphine ligands may be used to provide greater catalyst deactivation stabilization. however, with a much lower rate inhibition of the hydroformylation reaction than with the n-alkyldiphenylphosphine ligands compared to that obtained with triphenylphosphine. US Patent No. 4,400,548 states that ligands of the bisphosphine monoxide type can be used to prepare rhodium complex catalysts with improved thermal stability useful in the production of aldehydes by hydroformylation. However, despite the obvious advantages, according to the above-mentioned literature data, there is still a search for a more effective phosphorus ligand which would provide a more active, more stable and / or more versatile metal-phosphorus ligand complex catalyst. So far, this research is limited, unlike the present invention, mainly on the use of triorganophosphine and triorganophosphite ligands. The method of hydroformylation of an ethylenically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a catalyst constituting a complex of a transition metal from group VIII with a phosphate ligand to form aldehydes according to the invention consists in that the hydroformylation of an ethylene compound is carried out in the presence of a catalyst that is a complex consisting of a complex consisting of with carbon monoxide and a diorganophosphite ligand of formula I, wherein W is an alkyl radical of 1-18 carbon atoms optionally containing one or more phenyl, cyano, halogen, nitro, trifluoromethyl, hydroxyl, amine, -COR6, where R6 represents an alkyl group of 1-10 carbon or phenyl atoms, carbonyloxy, oxycarbonyl, amide, sulfonyl, sulfinyl, silyl, ether, phosphonyl, thionyl, alpha-naphthyl radical, beta-naphthyl radical or radical of formula 6, in which X1, X2 and Z4 is a hydrogen atom, an alkyl, phenyl, benzyl, cyclohexy radical 1-methylcyclohexyl, cyano, halo, nitro, trifluoromethyl, hydroxy, amine, -COR6, where R6 is as defined above, carbonyloxy, oxycarbonyl, amide, sulfonyl, sulfinyl, silyl, ether or thionyl, phosphonyl radicals and Ar, the same or different, represents an aryl radical substituted with one or more substituents as given above for X1. X2 and Z4, each Q is a divalent bridging group, such as a group of formula -S- or -CR1R2- in which R1 and R2 are each individually hydrogen or an alkyl radical of 1-12 carbon atoms, and n is the number 0 or 1 or a diorganophosphite ligand of formula 5 is used, wherein Q is -CH2- or -CHCH3-, each R6 is an alkyl radical of 1-10 carbon atoms, Y1 and Y2 are each hydrogen, a branched chain alkyl radical containing 3 - 12 carbon atoms, phenyl, benzyl, cyclohexyl and 1-methylcyclohexyl groups, W is an aryl radical of formula 6, where X1, X2 and Z4 are each hydrogen, an alkyl radical of 1-18 carbon atoms, optionally substituted 150 429 3 an aryl, alkaryl, aralkyl and alicyclic radical, a cyano group, a halogen or an ether group, but simultaneously at least two X1 and X2 or at least two Y1 and Y2 in a given ligand are hindered radicals in the form of an isopropyl group or greater, as well as with in that no more than three X1, X2, Y1 or Y2 are a hindered radical of an isopropyl group or more, and in the presence of the added free diorganophosphite ligand of Formula 1 or 5. In the process according to the invention, the decomposition of the free diorganophosphite ligand is reduced by means of a / removing a portion of the liquid hydroformylation reaction medium from the formylation reaction zone, acting on the low-base ammonite resin liquid environment thus removed, and returning the treated reaction environment to the reaction zone. Preferably, the hydroformylation reactions are conducted with continuous recycle of the catalyst-containing fluid. Thus, part of the liquid hydroformylation reaction medium is removed from the hydroformylation reaction zone and the medium is passed either before and / or after separation of the aldehyde compound therefrom, through a bed of weakly basic anion exchange resin. Third-order cross-linked is used as the weakly basic anion exchange resin. amine polystyrene anion exchange resin of gel or macroreticulum type. And so e.g. The diorganophosphite ligands used in the process of the invention improve the catalytic activity and the catalyst and ligand stability in hydroformylation reactions, even when using less active olefins such as isobutylene and internal olefins. Takwiec e.g. The high catalytic activity of the diorganophosphite ligands makes it possible to carry out the hydroformylation reaction of olefins at a temperature lower than the temperature generally considered favorable when using conventional ligands such as triorganophosphines. Similarly, in the hydroformylation of olefins, enhanced ligand and catalyst stability can be achieved by the use of diorganophosphite ligands, such as reaction stability with the produced aldehyde, stability in terms of hydrolysis resistance and stability in terms of ligand resistance as compared to hydrogenolize ligand resistance. trioorganophosphite. In addition, the use of diorganophosphite ligands in the method of the invention provides an excellent method of controlling the compound production selectivity in hydroformylation reactions. And so e.g. In the production of oxidized products such as aldehydes with a very low ratio of normal to iso (branched chain) compounds, diorganiphosphites have been found to be very effective ligands. Moreover, it has been found that the diorganophosphite ligands used in the process according to the invention not only constitute compounds which provide excellent catalytic activity, but also both catalyst stability and ligand stability in the hydroformylation reaction of unobstructed cr-olefins and also olefins of the type. less active, such as the spatially hindered α-olefins, e.g. isobutylene and internal olefins, but also that they are particularly useful for providing such catalyst activity and, at the same time, the stability of both the catalyst and the ligand in the hydroformylation of mixtures of α-oleins and internal olefins used as starting compounds. As can be seen from formula 1, the diorganophosphite ligands used in the process of the invention constitute a group of compounds completely different from the triorganophosphite ligands. The diorganophosphores used in the process according to the present invention contain only two organic radicals bound to the phosphorus atom via oxygen, one of the organic radicals mentioned being bound by two phenolic oxygen atoms (but the oxygen atom is bound to a separate radical aryl) and the second organic radical is bound by a single phenolic or alcoholic oxygen atom. Triorganophosphites contain three organic radicals, each radical being bound to the phosphorus atom through its own oxygen atom. It is also in the case of hydrolysis that the diorganophosphite ligands used in the process of the invention give both a biphenol compound in which each phenolic oxygen atom is bound to a separate aryl radical, and a monool type compound, while the triorganophosphite ligands give a monool type equivalent of the three compounds. More preferably, the invention includes the use of a rhodium-diorganophosphite ligand complex catalyst and free organophosphite ligand in the preparation of aldehydes, reacting the olefinic compound with carbon monoxide and hydrogen. The aldehydes produced correspond to those obtained by the addition of a carbonyl group to an ethylenically unsaturated carbon atom in the starting compound with simultaneous saturation of the ethylene bond. Such preferred methods are known in the industry under various names such as method or reaction, oxo, oxonation, Roelen reaction, and more commonly hydroformylation. And so e.g. The hydroformylation may preferably be carried out in a continuous, semi-continuous or stationary manner. It may, if desired, include the recycle of liquid and / or gas. Likewise, the method or order of adding the components of the reaction mixture, catalyst and solvent is also not critical and the addition may be made in any conventional manner. In general, the hydroformylation reactions are preferably carried out in a liquid reaction medium containing a catalyst solvent, preferably a solvent in which both the ethylenically unsaturated compound and the catalyst are soluble. Besides, as is the case with the known hydroformylation processes, which use a rhodium-phosphorus complex catalyst and free phosphorus ligand, it is highly preferred that the hydroformylation reactions according to the invention are carried out in the presence of free diorganophosphite ligand and in the presence of a composite catalyst. By "free Ugand" is meant a diorganophosphite Ugand not complex with rhodium. A more preferred method of hydroformylation according to the invention is the selective hydroformylation, improved over the hydroformylation reactions involving known catalysts constituting the rhodium-phosphorus ligand complexes, made possible by the improved activity of the catalyst and, at the same time, the improved stability of the catalyst and the ligand, as well as obtained by using the diorganophosphite ligands used in the process according to the invention, in contrast to the triorganophosphite and triorganophosphine ligands previously used in the art. It should be noted that the successful outcome of the process of the invention is not dependent on, and is not exaggerated in advance, the detailed structure of a catalytically active metal complex, which may be single-core, dual-core and / or multi-core. In fact, the exact structure of the active form is unknown. Although the present specification is not intended to be related to any theory or mechanistic dispute, it appears that the catalytically active complexes may in their simplest form essentially constitute a complex association of rhodium with carbon monoxide and a diorganophosphite ligand. The term "complex" means a coordination compound formed by the association of one or more electron-rich molecules or atoms capable of independent existence with one or more electron-poor molecules or atoms that are also capable of independent existence. The diorganophosphite ligands used in the process according to the invention, which contain the element phosphorus, have one free or free pair of electrons and are therefore capable of forming a coordination bond with rhodium. As can be seen from the foregoing discussion, carbon monoxide, which also properly classifies as Uganda, is also present and is complex with rhodium as well. The final active composite catalyst composition may also contain additional organic ligand or an anion saturating the coordination centers or the nucleus charge of the rhodium atom, as is the case with the conventional catalysts of the prior art group VIII-triorganophosphine or phosphite transition metal complex. The organic ligands and anions mentioned by way of illustration include such ligands and anion as hydrogen "(H ~), halogen" (Cl ", Br", J "), alkyl", aryl ", substituted aryl", CF3 ~, C2F5 ", CN", R2PO "and RP / O // OH / O" (wherein each R is alkyl or aryl), acetate ", acetylacetonate", SO22 ", PF4", PF6 ", NO2", NO3 " , CH3O ", CH2 = CHCH2 ~, CeHsCN, NO, NH3, pyridine, / C2H5 / 3N, mono-olefins, diolefins and triolefins, tetrahydrofuran etc. It will be appreciated that the active complex is preferably free of additional organic ligand or anion which could poison the catalyst and have an inappropriate, detrimental effect on the performance of the catalyst. And so e.g. it is known that in typical rhodium-catalyzed hydroformylation reactions, the catalyst can be poisoned by halogen anions and sulfur compounds. The active catalysts used in the process according to the invention are also preferably free of halogen and sulfur directly bound to rhodium. 150 429 5 The number of lineage coordination centers available is well known in the art and may range from 4-6. For clarification, it can be stated that the preferred rhodium active catalyst used in the process of the invention contains, in its simplest form, a total of four moles of diorganophosphite ligand and carbon monoxide in complex combination with one mole of rhodium. Thus, the active catalysts may be a mixed complex catalyst, in monomeric, dimeric or multicore form. They are characterized by the presence of one, two and / or three diorganophosphite molecules complexed with a single rhodium atom. As noted above, carbon monoxide which is complexed with rhodium in the active complex is also present. Moreover, as is the case with the known hydroformylation reactions catalyzed by rhodium-triorganophosphine or phosphite ligand complexes, where it is generally believed that active catalysts also contain hydrogen directly bound to rhodium, it is likewise considered that the active complex of the preferred rhodium catalyst used is The method of the invention also may contain complexed hydrogen in addition to the diorganophosphite ligand and the carbon monoxide ligand. Indeed, it is believed that the active complexes in the rhodium catalysts used in the process according to the invention may also contain hydrogen in addition to the diorganophosphite ligand and the carbon monoxide ligand, especially considering the presence of hydrogen gas which is used in this process. Regardless of whether the active complex catalyst is formed prior to introduction into the sphere of the carbonylation reaction or the active complex is formed in situ during the carbonylation reaction, it is preferred that the hydroformylation reactions are carried out in the presence of free diorganophosphite ligand. By way of illustration, the final catalytic composition with an active rhodium complex can be compared, or determined, by the results of parallel reactions occurring between the diorganophosphite and carbon monoxide ligands for complexing and coordination centers and the element rhodium. Parallel reactions can be disturbed or influenced to a wide extent by increasing or decreasing the concentration of the diorganophosphite ligand. In general, a component (carbon monoxide or diorganophosphite ligand) that can shift the equilibrium of parallel reactions to its advantage should have a greater ability to occupy coordination or complexing centers. And so e.g. , one may consider the function of the free diorganophosphite ligand either as maintaining the status quo for the various forms of the active catalyst complex during hydroformylation or as a means of shifting the equilibrium of parallel reactions to its advantage and thus causing the placement of additional diorganophosphite ligands on the rhodium phosphite complex. with supposed removal of a similar amount of carbon monoxide ligands from the composite catalyst. The diorganophosphite ligands used in the process according to the invention are preferably compounds of general formula I, where W is an optionally substituted alkyl, aryl, alkaryl, aralkyl and alicyclic radical, each Ar being the same or a different, optionally substituted aryl radical, each y represents the number 0, Q is a divalent bridging group such as -CR1R2- or -S-, R1 and R2 are separately hydrogen, an alkyl radical of 1-12 carbon atoms, such as methyl, propyl, isopropyl, butyl, isodecyl, dodecyl, etc., and n is the number 0-1. Moreover, when n is 1, Q is preferably a -CR1R2 bridging group as defined above, more preferably a methylene or alkylide group of the formula -CHR2-, in which R2 is an alkyl radical of 1-12 carbon atoms, in particular a methyl group . Preferably, W is a substituted or unsubstituted alkyl or aryl radical. The more characteristic W hydrocarbon radicals include primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, 11th order. butyl, Ill-row. -butyl, III-row. butylethyl, III-row. butylpropyl, n-hexyl, amyl, Ql-order. amyl, tertiary, amyl, isooctyl, 2-ethoxyhexyl, decyl, octadecyl etc. aryl radicals such as phenyl, naphthyl, anthracyl, etc. , aralkyl radicals such as benzyl, phenylethyl, etc. , alkaryl radicals such as tolyl, xylyl etc. , and alicyclic radicals such as cyclopentyl, cyclohexyl, cyclooctyl, cyclohexylethyl, etc. Preferably, the unsubstituted alkyl radicals have 1-18, especially 1-10, carbon atoms, while the unsubstituted aryl, aralkyl, alkaryl and alicyclic radicals preferably have 6-18 carbon atoms. The aryl radicals mentioned include optionally substituted aryl radicals. Such aryl radicals contain 6-18 carbon atoms and can be, for example, phenylene (C6H4), naphthylene (C10H6), anthracylene (C14H8) etc. The substituents of the W radicals as well as the aryl groups of Ar include monovalent radicals of the same type as substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl and alicyclic radicals and silyl radicals of the formulas -Si / R6 / 3 and -Si / ÓR6 / 3, amino radicals such as the group of formula -N / R6 / 2, acyl radicals such as the group of formula -C / O / R6, carbonyloxy radicals such as the group of formula -C / O / OR6, oxycarbonyl radicals such as like a group of formula - OC / O / R6, amide radicals such as groups of formula -C / O / N / R6 / 2 and -N / R6 / C / O / R6, sulfonyl radicals such as a group of formula - S / O / 2R6, sulfinyl radicals such as the -S / O / R6 group, ether (i.e. oxyl) radicals such as the -OR6 group, thionyl ether radicals such as the -SR6 group, phosphonyl groups such as -F / O // R6 / 2 'and halogen, nitro, cyano, trifluoromethyl and hydroxyl etc. in which R6 separately represents the same or different substituent or unsubstituted monovalent hydrocarbon radical with the meaning given for the symbol W, except that in the case of amino substituents such as the group of formula -N / R6 / 2, R6 together may also denote divalent bridging groups, forming a heterocyclic radical with a nitrogen atom, and in the case of amine and amide substituents, such as groups of the formula -N / R6 / 2, -C / 0 / N / R6 / 2 and -N / R6 / C / O / R6, each -R6 bonded to N- may also be hydrogen, and in the case of phosphonyl substituents such as the group of formula -P / O // R6 / 2, one of the symbols R6 may also be hydrogen. Preferred monovalent hydrocarbyl substituents, including R6 radicals, are unsubstituted alkyl or aryl radicals, although, if desired, they may be substituted with a substituent that does not adversely affect the reaction, such as e.g. hydrocarbyl and non-hydrocarbyl radicals used as the substituents set out above. Among the more characteristic unsubstituted monovalent hydrocarbon radicals used as substituents, including those radicals R6 which may be bound to the monovalent hydrocarbon radicals W and / or Ar in the diorganophosphite formula above defined, which may be mentioned here are alkyls including primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, II-order. butyl, III- row butyl, Ill-row. butyl ethyl, 3rd order butylpropyl, n-hexyl, amyl, 2nd order amyl, 3rd order amyl, isooctyl, decyl, etc. aryl radicals such as phenyl, naphthyl, etc. aralkyl radicals such as benzyl, phenylethyl, triphenylmethylethane, etc. alkaryl radicals such as tolyl, xylyl groups etc. , and alicyclic radicals such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, cyclohexylethyl, etc. The more characteristic non-hydrocarbyl substituents given by way of illustration which may be present in the monovalent hydrocarbon radicals W and / or Ar in the diorganophosphite formula as defined above, include, for example, halogen, preferably chlorine or fluorine, -NO2-, -CN, -CF3, -OH, -Si / CH3 / 3, -Si / OCH3 / 3, Si / CH3H7 / 3, -C / O / CH3, -C / O (C2H5, -OC / 0 / C6H5, -C / O / OCH3, -N / CH3 / 2, -NH2, -NHCH3, -NH (C2H5), -CONH2, -CON (CH3 / 2); - S / O / 2 / C2H5, -OCH3, - OC6H5, -C / 0 / C6H5, -O / III-order C4H9 /, -S02H5, - OCH2CH2OCH3, - / OCH2CH2 / 2 OCH3, - / OCH2CH2 / 3OCH3, -SCH3, -S / 0 / CH3, -SC6H5, - P / 0 // C6H5 / 2, -P / 0 / / CH3 / 2, -P / O // C2H5 / 2, -P / 0 / C3H7 / 2, - P / O // C4H9 / 2, -P / 0 // C6H13 / 2, -P / 0 / CH3 (C6H5), -P / O // H // C6H5), -NHC (O) CH3, group of formula 7, group of formula 8, group of formula 9, group of formula 10, etc. In general, substituents for monovalent hydrocarbon radicals W and Ar in the diorganophosphite formula defined above may also contain from 1 to 15 carbon atoms and may be combined with monovalent hydrocarbyl radicals W and / or Ar in any form 7 of the appropriate position as in the case of bridge groups of formula Q connecting two groups of the symbol Ar in the diorganophosphite formula as above. In addition, each radical of the symbols Ar and / or W may contain one or more such substituents, which substituents may also be the same or different. In preferred diorganophosphite ligands, the two Ar groups linked by the bridging group Q are linked in their ortho position to the oxygen atoms linking the Ar groups to the phosphorus atom. It is also preferred that a substituent radical for Ar groups, including an aryl radical W, is bonded to the pair and / or ortho position of the aryl group with respect to the oxygen atom bonding the substituted aryl group to the phosphorus atom. Accordingly, a preferred group of the diorganophosphite ligands used in the process of the invention are ligands wherein W is a substituted or unsubstituted alkyl radical. Preferred alkyl radicals include unsubstituted alkyl radicals having 1-18 carbon atoms, more preferably 1-10 carbon atoms, such as those defined above and alkyl radicals substituted with a non-hydrocarbyl substituent, e.g. silyl radicals of the formula -Si / R6 / 3 and -Si / OR6 / 2, acyl radicals of the formula -C / O / R6, carbonyloxy radicals of the formula -C / O / OR6, oxycarbonyl radicals of the formula -OC / O / R6 , amide radicals of the formula -C / 0 / N / R6 / 2 and -N / R6 / C / O / R6, sulfonyl radicals of the formula -S / O / 2R8, sulfmyl radicals of the formula -S / O / R0, ether (i.e. oxyl) radicals of the formula -OR6, thionyl ether radicals of the formula -SR6 and phosphoryl radicals of the formula -P / 0 // R6 / 2 in which the formulas R6 is as defined above, as well as halogen, nitro , cyano, trifluoromethyl and hydroxyl, etc. The electronegatically substituted alkyl radical has the potential to form a weak coordination bond with the rhodium complex, and such substituents can impart, during the hydroformylation reaction, greater catalytic stability to the rhodium-diorganophosphite catalyst. The most preferred electronegative substituted alkyl radicals have the formula [C / R7 / 2] pP / 0 // R6 / 2, where R is as defined above, R7 are the same or different and represent hydrogen and an alkyl radical of 1-4 atoms carbon, and p is a number 1-10, in particular the formula [/ CH2 /] PP / 0 // R6 / 2 where p is a number 1-3 and R6, the same or different, represents an alkyl radical of 1-4 carbon atoms , a phenyl or cyclohexyl group, with the proviso that one R6 may be hydrogen. The diorganophosphite ligands of this type used in the process of the present invention and the methods of their preparation are known in the art. And so e.g. a typical method of producing such ligands involves reacting a suitable organic diphenyl compound such as 2,2'-dihydroxybiphenyl with phosphorus trichloride to form an organic phosphorochloridine type intermediate such as 1,1β-biphenyl-2,2'-diylphosphorochloridine which in turn is reacted with a suitable monohydroxy compound such as 2,6-di-tertiary. butyl-4-methylphenol, in the presence of an HCl acceptor such as an amine to give a diorganophosphite ligand such as 1, [beta] -biphenyl ^^^ yl- ^ i-di-HI-order. -butyl- 4-methylphenol / phosphite. Possibly, these Ugandans can also be produced, e.g. from previously prepared organic phosphorodichloridite such as 2,6-di-III-order phosphorodichloridite. butyl-4-methylphenyl, and a suitable diphenol compound such as 2,2'-dihydroxybiphenyl in the presence of a HCl acceptor such as an amine to give a di-organophosphite ligand such as 1,1'-biphenyl-2,2'-diyl - / 2,6d-III-row butyl-4-methylphenyl / phosphite. Accordingly, ligands of general formula II are preferably used in which Q represents a group of formula -CR1R2 in which R1 and R2 are each individually hydrogen, an alkyl radical with 1-12 carbon atoms, such as methyl, propyl, isopropyl , butyl, isodecyl, dodecyl etc. , phenyl, tolyl and anisyl groups, and n is 0-1, and Y1, Y2, Z2, and Z3 each individually represent hydrogen, an alkyl radical of 1-18 carbon atoms, an optionally substituted aryl, alkaryl, aralkyl and alicyclic radical with the proviso that both Y1 and Y2 are hindered radicals in the form of an isopropyl group, more preferably in the form of a III-row group. -butyl or greater, and W is an optionally substituted alkyl radical, especially preferably having 1-10 carbon atoms. Preferably, Q is a methylene bridging group - (CH2-) or an alkylidene bridging group ACHR2), wherein R2 is an alkyl radical of 1-12 carbon atoms, especially ACHCH3-). Preferred ligands are those of formula II in which both Y1 and Y are III-row radicals. butyl groups, Q is -CH2- and W is an unsubstituted alkyl radical of 1-8 carbon atoms, especially compounds of formula II in which Y1 and Y2 are M-order radicals. butyl groups, Q is -CH2- and W is an alkyl radical substituted with a phosphonyl group of the formula -CH2-PO / R3 / 2 in which R3 is the same or different and separately represents an alkyl or phenyl group, one of R3 may also be hydrogen such as the compound of formula II, in which W is a radical of formula CH2P (O) / CeH4, and the other symbols have the meanings given above. In a preferred embodiment of the process according to the invention, the olefinic starting material is butene-1, butene-2, isobutylene and a mixture of nineolefins consisting essentially of butene-1 and butene-2, and the phosphorus ligand is the compound of formula II in which Q is -CH2 - or -CHCH3, Y1 and Y2 are branched alkyl radicals with 3-5 carbon atoms and W is an unsubstituted alkyl radical with 1-10 carbon atoms. It is further noted that in the case of rhodium catalyzed hydroformylation reactions when a diorganophosphite ligand in which W is an aryl radical is used, the substitution (except for the substitution caused by the bridging group of the ortho-aryl group W and the two Ar groups in formula 1) i.e. the ortho position to the oxygen atom connecting each aryl group to the phosphorus atom of the diorganophosphite ligands) can affect the catalytic activity and / or the stability of the ligand. Obviously, the spatial obstacle around the phosphorus atom in the diorganophosphite ligand caused by the ortho substitution of all aryl groups in such positions affects the stability of the ligand and / or the catalytic activity, in particular as regards the hydroformylation reactions carried out in the presence of the free phosphorus ligand used. excess. And so e.g. diorganophosphite ligands in which all the aryl groups are unsubstituted (too small a hindrance) and diorganophosphite ligands in which four of the total number of such ortho positions in aryl groups are substituted with a radical having an isopropyl group or more (too large a hindrance) sterilization) are not preferred because of the low stability and / or catalytic activity of the ligand that is obtained during their use, especially in the presence of excess free ligand. On the other hand, in the case of rhodium catalyzed hydroformylation, an improvement in ligand stability and / or catalytic activity, even in the presence of excess free ligand, can be obtained if at least two of the total such ortho positions in all aryl groups of the diorganophosphite ligand are displaced are a radical having a hindered isopropyl group, preferably a tertiary group. butyl or more, but simultaneously no more than three, and preferably no more than two of the total number of such ortho positions in all aryl groups are substituted by a hindered radical in the form of an isopropyl group or greater. In addition, the diorganophosphite ligands of which two ortho positions of the two Ar groups in general formula 1 are available are substituted with an isopropyl hindered radical, or more preferably tertiary. butyl or greater, have a better ligand stability (and this is a general rule) than the diorganophosphite ligands, which were thus substituted at two such available ortho positions of the aryl groups with the symbol W. Moreover, in preferred diorganophosphite ligands, catalytic activity and / or stability can be further enhanced by substituting said ortho positions of an aryl radical with the symbol W with an electronegative substituent, such as a cyano group, with the ability to form a weak coordination bond with a group VIII metal transition metal. Another preferred group of diorganophosphite ligands used in the process according to the invention are ligands of formulas 3 and 4, in which Q is a group of formula -CR1 R2, in which R1 and R are separately hydrogen, an alkyl radical of 1-12 carbon atoms, and n is the number 0-1, X1, X2, Y1, Y2, Z1, Z2 and Z3 each individually represent hydrogen, an alkyl radical of 1-18 carbon atoms, a substituted or unsubstituted aryl, alkaryl, aralkyl and α-cyclic groups such as phenyl, benzyl , cyclohexyl, 1-methylcyclohexyl etc. , hydroxy, carbonyloxy and ether, provided that simultaneously at least two radicals X1 and X2 or at least two radicals Y1 and Y2 are hindered radicals in the form of an isopropyl group or more, and also that in formula III, no more than three radicals such as X, X2, Y1 or Y2 are hindered radicals in the form of an isopropyl group or more, in particular compounds of formula III or 4 in which Q is -CH2- or -CHCH3 - and Y1 and Y2 are branched chain alkyl radicals containing 3-5 carbon atoms. In this case, in a preferred embodiment of the process according to the invention, butene-1, butene-2 and isobutylene are used as the olefin starting material, and an olefin mixture consisting essentially of butene-1 and butene-2, and a compound of formula 3 or 4 in which Q is -CH2- and X1, X2, Y1, Y2, Z1, Z2 and Z3 are each individually hydrogen, an alkyl radical of 1-8 carbon atoms, hydroxyl, carbonyloxy and ether. Yet another preferred group of diorganophosphite ligands are the novel compounds of formula 5, wherein Q is -CH2- or -CHCH3- * R8 is an alkyl radical of 1-10 carbon atoms, Y1 and Y2 are each individually hydrogen, a branched chain alkyl radical of 3-12 W is an alkyl radical of 1-12 carbon atoms, or an aryl radical of formula 6, where X1, X2 and Z4 are each individually hydrogen, an alkyl radical of 1-18 carbon atoms, a substituted or unsubstituted aryl radical , alkaryl, aralkyl and alicyclic, cyano, halogen, ether, provided that simultaneously at least two X1 and X2, or at least two Y1 and Y2 in a given Uganda are hindered radicals, in the form of an isopropyl group or greater and also with the fact that no more than three X, X2, Y1 or Y2 are hindered radicals in the form of an isopropyl group or more, in particular compounds of formula S, in which R6 is an alkyl radical with 1-10 carbon atoms , Y1 and Y2 are a branched chain alkyl radical of 3-5 carbon atoms, and W is an alkyl radical of 1-10 carbon atoms, most preferably the compounds of formula 5 where Z2 and Z3 are methoxy, Y1 and Y2 each represent radical III -before butyl and W is a methyl radical. The most preferred diorganophosphite ligands are the ligands of formula II, in which Z2 and Z3 represent hydroxyl or methoxy groups, and in particular methoxy groups, Y1 and Y2 represent a branched chain alkyl radical with 3-5 carbon atoms, especially group III-order. butyl, W is an alkyl radical of 1-10 carbon atoms and an aryl radical of formula 11, where Z4 is hydrogen or a methoxy group, especially hydrogen, Q is a bridging group of the formula -CR1R2- as defined above, n is 0-1 . Preferably W is a methyl radical. The diorganophosphite ligands used in the method according to the invention include ligands with the formula: 13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31 , 32.33.34.35, 36.37.38.39,40.41.42.43.44.45.46.47.48.49.50.51.52.53.54.55.56 , 57.58.59.60.61.62.63, 64.65.66.67.68.69.70.71 and 72, preferably compounds of formula 12, 12a and 12b, where Q is -CH2 -, an stands for Learning 0 or 1. In the formulas mentioned, t -Bu represents a tertiary butyl radical, Ph represents a phenyl radical (-CeHs) and (-C9H19) represents a branched-chain mixture of nonyl radicals. The most preferred diorganophosphite ligands used in the process of the invention are 1, r-biphenyl-2,2'-diyl- (2,6-di-tertiary). butyl-4-methylphenyl / phosphite (formula 29), phenyl [3,3 ', 5,5'-tetra-tertiary. butyl-1,1'-biphenyl-2,2'-diyl] phosphite (formula 30), 1,1'-binaphthylene-2,2'-diyl (2,6-di-tertiary). butyl-4-methylphenyl / phosphite (formula 31) and methyl [3,3'-di-tertiary. butyl-5,5H-dimethoxy-1,1,1-biphenyl-2,2'-diyl] phosphite. The diorganophosphite ligands as defined above are used in the process of the invention as phosphorus ligands in the rhodium-based catalyst composition, and also as environment-free ligands. In addition, normally the phosphorus ligand constituting the rhodium-diorganophosphite catalyst and the free phosphorus ligand present in an excess present in the reaction carried out according to the invention, preferably present in excess, constitute the same type of diorganophosphite ligand, or alternatively, diorganophosphite ligands may be used. of various types as well as mixtures of two or more of the diorganophosphite ligands. As with the rhodium-phosphorus complex catalysts of the prior art, the rhodium-diorganophosphite complex catalysts used in the process of the invention can be prepared by methods known in the art. And yes, e.g. , it is possible to pre-form carbonyl (diorganophosphite) catalysts with rhodium and then introduce them into the hydroformylation reaction environment. Advantageously, the rhodium diorganophosphite complex catalysts can be derived from a metallic catalytic precursor that can be introduced into the reaction environment to form an active catalyst in situ. And so e.g. Catalytic rhodium precursors such as rhodium dicarbonyl acetylacetate, Rb2C3, Rhe / CO2 / i2, Rhe / CO / ie, RI1 / NO3 / 3 etc. can be incorporated into the reaction medium to form the active catalyst in situ to form the reaction medium. together with the diorganophosphite ligand. Preferably, dicarbonylodine acetylacetonate is used as the rhodium precursor and is reacted in the presence of a solvent with diorganophosphite to form the rhodium-carbonyl catalytic precursor, which is then introduced into the reactor together with the excess organophosphite ligand. receiving active catalyst in situ. In any event, it is sufficient for the process according to the invention that the carbon monoxide, hydrogen and diorganophosphite are ligands capable of being complexed with rhodium and that, under hydroformylation conditions, a rhodium-diorganophosphite catalyst is present in the reaction medium. Accordingly, the catalysts used in the process of the invention, which are rhodium diorganophosphite complexes, may be defined as complexes consisting essentially of rhodium with carbon monoxide and a diorganophosphite ligand. Of course, it should be understood that the term catalyst "consisting essentially of" should not be understood as excluding, but rather as including, metal complexed hydrogen, particularly in the case of rhodium catalyzed hydroformylation reactions, in addition to the oxide and the diorganophosphite ligand. Furthermore, this term is not to be understood as excluding the possibility of the presence of other organic ligands and / or anions which may also be complexed with the metal. However, such terms for a catalyst include the presence of other substances in amounts at which they can poison or inactivate the catalyst, it is also most desirable that it be free of impurities such as rhodium-bound halogen in the form of e.g. chloride, etc. As mentioned, the hydrogen and / or carbonyl ligands in the rhodium-diorganophosphite complex catalyst may be present as a result of being ligands bound to the catalytic precursor and / or formed in situ, e.g. due to the presence of hydrogen gas and carbon monoxide gas used in the hydroformylation reaction. Moreover, as in the case of the known catalysts constituting the group VIII transition metal complexes - phosphorus ligand, it is known that the amount of catalyst in the reaction environment in the process according to the invention must be only the smallest amount necessary to ensure the concentration of rhodium required for a given application and constitute the basis for what least of this catalytic amount of rhodium to catalyze a particular carbonylation reaction desired. One of the advantages of the process according to the invention is that an overall improved catalytic activity is achieved by the use of diorganophosphite ligands. The improved catalytic activity can be translated into significant processing advantages, especially when scarce and expensive rhodium is used, since a lower reaction temperature and / or a lower amount of catalytically active metal can be used compared to catalysts with lower activity. Generally, rhodium concentrations in the range of about 10-1000 ppm, based on free metal, are sufficient for most reactions. In general, it is preferred to use about 10-500 ppm of rhodium, in particular 25-350 ppm of rhodium, based on the free metal. The starting olefin compounds used in the process of the invention may be end or intrinsically unsaturated and may be straight chain or branched compounds or cyclic compounds. Such olfins contain 2-20 carbon atoms in the molecule and have one or more ethylenically unsaturated groups. In addition, these olefins may contain groups or substituents which do not significantly interfere with the hydroformylation reaction, namely, groups such as carbonyl, carbonyloxy, oxyl, hydroxy, oxycarbonyl, halogen, alkoxy, aryl, haloalkyl, etc. The explanatory olefinic unsaturated compounds include: or-olefins, internal olefins, alkyl alkanecarboxylates, alkenyl alkane carboxylates, alkenyl alkyl ethers, alkanols, etc. , such as e.g. ethylene, propylene, butene-1, hexene-1, octane-1, decene-1, dodecene-1, octadecene-1, butene-2, 2-methylpropane (isobutylene), isoamylene, pentene-2, hexene-2, hexene -3, heptene-2, cyclohexene, propylene dimers, trimers and tetramers, 2-ethylhexene-1, styrene, 3-phenylpropene-1, hexadiene-1,4, octedien-1,7,3-cyclohexylbutene-1, aluminum alcohol, hexene-1-ol-4, octene-1-ol-4, vinyl acetate, IM 429 11 allyl acetate, 3-butylene acetate, vinyl propionate, allyl propionate, allyl butyrate, methyl methacrylate, ethyl ether, ethyl ether, ether allyl ethyl, 7-n-propyl heptenecarboxylate, 3-butenenitrile, 5-hexenamide etc. Optionally, mixtures of various olefinic starting compounds can also be used in the process according to the invention. More preferably, the process of the invention is particularly useful for the preparation of aldehydes by hydroformylation of 2-20 carbon alpha-olefins and internal 4-20 carbon olefins, as well as mixtures of alpha-olefins with internal olefins. The most preferred olefins are butene-1, butene-2 (cis and / or trans), isobutene, and mixtures thereof. The process according to the invention is preferably also carried out in the presence of an organic catalyst solvent. Any solvent that does not interfere with the process can be used, and such solvents also include solvents that are commonly used in the known reactions catalyzed with a group VIII transition metal. For clarification, it can be added that the solvents suitable for use in the rhodium-catalyzed hydroformylation reactions include those disclosed e.g. in U.S. Patent Nos. 3,527,809 and 4,148,830. Of course, you can use mixtures of different solvents. In general, in the rhodium catalyzed hydroformylation reaction as the primary solvent, compounds of the aldehyde type are preferably used which correspond to the aldehydes produced and / or the higher boiling aldehyde liquid condensation byproducts, such as the above boiling aldehyde liquid condensation by-products which are generated in situ in reaction. Indeed, while at the start of the continuous process any suitable solvent may be used, if desired, with aldehyde compounds corresponding to the aldehydes produced being preferred, the primary solvent may contain aldehyde products and higher boiling aldehydes liquid by-products as a result of condensation products the nature of such continuous processes. These aldehyde condensation by-products can be preformed and used accordingly. In addition, such above-boiling aldehydes condensation by-products as well as methods for their preparation are fully disclosed in US Pat. Nos. 4,148,830 and 4,247,486. Of course, the amount of the solvent is not critical for carrying out the process according to the invention and must only provide a suitable reaction environment with a specific rhodium concentration for a given process. Generally, the amount of the solvent is in the range of about 5-95% by weight or more based on the total weight of the reaction medium. In general, it is preferred that the hydroformylation process of the invention is carried out continuously. Processes of this type are still known in the art and may include e.g. hydroformylation of olefinic intermediates with the use of carbon monoxide and hydrogen in a liquid homogeneous reaction medium containing a solvent, a rhodium-diorganophosphite catalyst and a free diorganophosphite ligand, introducing ready-to-react amounts of olefinic compounds of the reaction medium and hydrogen, maintaining the temperature of the reaction medium the reaction and pressure at a level suitable for the hydroformylation of the starting olefin compound and recovery of the reaction product by a known method. While the continuous process can be carried out in a one-time pass method, that is, in that a gaseous mixture consisting of unreacted olefin starting compound and aldehyde product gas is removed from the liquid reaction medium, and the final product is recovered from the liquid reaction medium. aldehyde and the reaction-ready olefinic starting compound, carbon monoxide and hydrogen are introduced into the liquid reaction medium for the next one-time pass, omitting to recycle the unreacted olefinic starting compound, in general it is also advisable to run a continuous process that includes recycling of either liquid and gas or both. Recycling operations of this type are known and may include either the recycle of a liquid, namely a rhodium-phosphite complex catalyst solution separated from a reaction product containing a given aldehyde, as disclosed in U.S. Patent 4,148,830, or gas recycle, as it was disclosed e.g. in U.S. Patent No. 4,247,486, or, if desired, a combination of both the recycle and gas recycle operations. The most preferred hydroformylation process according to the invention is the continuous recycle of the catalyst liquid. The product aldehyde can be recovered in a known manner, such as that described in U.S. Patent Nos. 4,148,830 and 4,247,486. 1 such as in a liquid catalyst recycle process, part of the liquid reaction solution containing the aldehyde product, catalyst, etc. , removed from the reactor, can be introduced into a vaporizer (a generator where the aldehyde product can be separated from the liquid reaction solution by distillation, in one or more stages, under normal, low or increased pressure, and then condensed and collected in a receiver product, and optionally subjected to further purification. The remaining, unvaporized catalyst, containing the liquid reaction solution, can then be recycled back to the reactor, such as other volatile substances such as e.g. unreacted olefinic compound together with hydrogen and carbon monoxide dissolved in the liquid reaction solution, after separation from the liquefied aldehyde product, e.g. by distillation. Generally, it is preferred to separate the product aldehyde from the rhodium catalyst-containing final solution under reduced pressure and temperature, e.g. less than 150 ° C and preferably less than 130 ° C. The process according to the invention is preferably carried out in the presence of free diorganophosphinic ligand, ie a ligand not complexed with rhodium. Preferably, the same free diorganophosphite ligand is used as the diorganophosphite ligand present in the rhodium-diorganophosphite complex catalyst, although the ligand may be different. The hydroformylation is carried out using any excess of free diorganophosphite ligand, i.e. using at least one molar free diorganophosphite ligand per mole of rhodium present in the reaction environment. However, it has been found that large amounts of free diorganophosphorus ligand are not necessary for the catalytic activity and / or stability of the catalyst in the rhodium catalyzed hydroformylation reaction and that they generally inhibit the activity of the rhodium catalyst. Accordingly, the process of the invention generally employs diorganophosphite ligands in an amount of about 4-50 and preferably 6-25 moles per mole of rhodium in the reaction environment. The amount of diorganophosphite ligand is the sum of the amount of diorganophosphite bound (complexed) with the source and the amount of free (non-complexed) diorganophosphite ligand present in the reaction. Of course, a reaction-ready diorganophosphite ligand can be introduced into the reaction medium of the hydroformylation process at any time and in any way in order to maintain a predetermined level of free ligand in the reaction medium. The possibility of carrying out the reaction according to the invention in the presence of a free diorganophosphite ligand is an important advantageous aspect as it eliminates the critical situation associated with the use of the ligand at very low, strictly defined concentrations, which is necessary in the case of certain complex catalysts, the activity of which can be inhibited, even if it is insignificant. the amount of free ligand, especially in the case of large-scale industrial process. Thus, the process manager obtains greater processing tolerance. The hydroformylation reaction conditions of the process of the invention are typical and include a reaction temperature of about 45-200 ° C, and a pressure of about 6.87-103Pa-68700 (XM03Pa. By using the rhodium-diorganophosphite complex catalysts in the process of the invention, the reactions can be carried out at a lower temperature than usual and at a higher speed. The process of the present invention can produce aldehyde products having a high ratio of normal aldehyde (i.e. straight chain aldehyde) to branched chain aldehyde, such as e.g. a ratio of about 5 to 1 or greater, however, in general, it is preferred to produce high branched-chain aldehyde products, i.e., one that exhibits a low straight-chain aldehyde to branched-chain aldehyde ratio, such as row 5 moU or less of n-aldehyde to 1 mole of branched-chain aldehyde. A unique feature of the process of the invention is the overall processing tolerance achieved in controlling the selectivity of the aldehyde product, provided by the use of diorganophosphite ligands. And so e.g. By isomerizing the olefinic starting compound in the hydroformylation reaction according to the invention with diorganophosphite ligands, it is possible to control or preselect a particular amount of branched chain aldehyde in the product, that is to say a preselection of the ratio of the amount of normal chain aldehyde produced can be selected. This is in contrast to the known hydroformylation reactions with phosphorus ligands, which show no or only little ability to isomerize the olefinic starting compound in a reaction of this type and there is no or only little possibility to control the ratio of normal aldehyde to aldehyde. about a branched chain. And so e.g. , alpha-olefins such as butene-1 can readily be hydroformylated by the process of the invention to provide an aldehyde product with a straight chain aldehyde to branched chain aldehyde ratio of less than 5 to 1, preferably less than 3 to 1, more preferably about 2 to 1. On the other hand, internal olefins can surprisingly be hydroformylated according to the process of the invention to obtain aldehyde products with an even higher content of branched chain isomers. For example , pure butene-2 can be hydroformylated to give a higher content of 2-methylbutanal, i.e. to obtain an aldehyde product in which the ratio of n-pentanal to 2-methylbutanal is about 2 to 1 or less, preferably less than 1 to 1, and more preferably less than 0.5 to 1. This processing tolerance in the process of the invention, due in part to the isomerization of the olefinic starting compound in the hydroformylation reaction and the choice of the diorganophosphite ligand to be used, is particularly useful in those cases where it is desired to optimize the production of the branched chain aldehyde. And so e.g. since the isoprene precursor that is used in the production of synthetic rubber is 2-methylbutanal, the possibility of producing essentially 2-methylbutanal directly by the method according to the invention is highly advantageous in the art in that it greatly facilitates the refining operations (separating from n- pentanal) and enables the production of larger quantities of the product, i.e. 2-methylbutanal for a given amount of the starting compound, i.e. butene-2. On the other hand, it is evident that it may be desirable to produce a branched-chain aldehyde product that is not rich in aldehyde, but that it may contain a normal aldehyde in a slightly higher proportion than that of a branched chain aldehyde, e.g. when the aldehydes are used to prepare alcohols and acids, which in turn are used e.g. for the production of synthetic lubricants, solvents, paints, fertilizers, etc. Likewise, mixtures of alpha-olefins and internal olefins can also be hydroformylated according to the method of the invention to obtain aldehyde products with a high content of branched chain isomers. And so e.g. the starting mixture of butene-1 and butene-2 can readily be hydroformylated to give an aldehyde product in which the ratio of straight chain aldehyde to branched chain aldehyde is about 3 to 1 or less, and more preferably about 2 to 1 or less. The possibility of simultaneous hydroformylation of both types of olefins, with comparable ease, from the same mixture of starting compounds is highly advantageous, as such starting materials of a-olefin and internal olefin mixtures are readily available and represent the most economical olefin feedstocks. In addition, the versatility of the diorganophosphite ligands used in the process of the invention facilitates the continuous hydroformylation of both α-olefins and internal olefins, and various reactors arranged in series can be used. This ability not only provides for the throughput tolerances of the hydroformylation in the second reactor of the unreacted olefin transferred to it from the first reactor, but also allows the reaction and hydroformylation conditions to be optimized e.g. a-olefins in the first reactor while optimizing the hydroformylation reaction conditions e.g. internal olefin in the second reactor. And so e.g. In the hydroformylation process of the present invention, the combined pressure of hydrogen, carbon monoxide and ethylenically unsaturated starting material is about 6.87-103-68700.0 (M03Pa. However, it is preferred that the hydroformylation process of the invention from olefins to aldehydes takes place under a combined pressure of hydrogen, carbon monoxide and ethylenically unsaturated starting material of less than 10305.00 · 103Pa, more preferably less than 3435.00-103 Pa. The minimum total pressure of the reactants is not particularly important and is usually limited by the amount of reactants necessary to achieve the desired reaction rate. More particularly, the partial pressure of carbon monoxide in the hydroformylation process of the present invention is preferably about 6.87 * 103 Pa and more preferably about 20.61-103 Pa -618.30-103 Pa, while the pressure is the molecular weight of hydrogen is preferably around 103.05-1099.20-103 Pa, preferably around 206.10-103 687.00-103 Pa, with 4-50 moles of diorganophosphite ligand being used per mole of rhodium. Generally, the mole ratio of hydrogen gas to carbon monoxide gas H2: CO a month ranges from about 1:10 to 100: 1, or may be higher, with a hydrogen to carbon monoxide mole ratio of from about 1: 1 to about 10: 1 being more preferred. . Further, the hydroformylation reactions of the present invention can be carried out at temperatures of about 45-200 ° C. Of course, the preferred reaction temperature for a given process depends on factors such as the type of olefin starting material, the type of metal catalyst used, and the desired yield. Temperature values for the hydroformylation reaction can also be assumed, however, the hydroformylation reaction according to the present invention can be optimized and the reactions carried out at a temperature surprisingly lower than that assumed to be preferred in the prior art. And so e.g. Compared with known rhodium-catalyzed hydroformylation systems, the improved catalytic activity and / or stability of the catalyst, which is obtained by the incorporation of the catalysts constituting the rhodium-diorganophosphite complexes, uniquely allows to achieve a high rate of selective hydroformylation reaction with a comparatively low reaction temperature. In general, for all types of olefinic starting materials, the preferred hydroformylation temperature is about 50-120 ° C. Advantageously, the α-olefins can be efficiently hydroformylated at about 60-110 ° C, while the olefins even less reactive than conventional α-olefins, such as isobutylene and internal olefins, as well as mixtures of α-olefins and internal olefins, are efficiently and preferably hydroformylated. at a temperature of about 70-120 ° C. Indeed, in the hydroformylation reaction according to the invention, no significant advantage is observed by adopting a reaction temperature much higher than about 120 ° C, which is considered less desirable, because of the possibility of reducing catalyst activity and / or rhodium loss. Although the hydroformylation reactions of the present invention may be carried out with any ethylenically unsaturated starting compound, such as those referred to above, the preferred hydroformylation method of the invention is used to convert olefins such as 2-20 carbon olefins. , and internal olefins with 4-20 carbon atoms in the molecule, as well as mixtures of such olefins into the corresponding aldehyde products. In addition, hydroformylation of olefins which are normally less reactive than the corresponding α-olefins without hindrance, such as isobutylene and internal olefins, is a most preferred aspect of the present invention than the hydroformylation of mixtures of α-olefins and internal olefins. The process according to the invention is used for the hydroformylation of olefins, in particular internal olefins and other less reactive sterically hindered olefins, such as isobutylene, using more active and stable catalysts than the catalysts prepared with the usual triorganophosphine ligands and thus possible obtaining faster reaction rates and / or increased amounts of aldehyde production at a much lower reaction temperature. The rhodium-catalyzed hydroformylation process of mixtures of α-olefins and internal olefins according to the invention is therefore unique in that it leads to the production of a high yield aldehyde product from a starting material containing both types of olefins, in contrast to the known processes, which are mainly characterized by the formation of hydroformylation products of only a more reactive compound. a-olefinic having no spatial hindrance. Of course, for the process according to the invention it is not decisive the proportionate preparation of the olefin mixture as the starting material, and mixtures containing these olefins in different proportions are also used as the starting olefin mixture. In general, mixtures of butene-1 and butene-2 (cis and / or trans) are subjected to hydroformylation, whereby these mixtures may optionally contain isobutene to give proportional mixtures of products consisting of mixtures of pentanal, 2-methylbutanal and, optionally, 3-methylbutanal. . Thereafter, side reactions during the rhodium-catalyzed hydroformylation process can be reduced with the aid of diorganophosphite ligands in terms of hindering the formation of an excessive amount of aldehyde by-product and in terms of the stability of the ligand to aldehyde production. And so e.g. While the use of a curdiorganophosphite ligand in the process of the present invention may reduce the excessive formation of higher boiling aldehyde condensation byproducts, it is evident that in the industrial continuous hydroformylation process of such olefins the concentration of higher boiling aldehyde condensation byproducts (e.g. dimeric and trimeric aldehydes) will eventually persist for some time until it finally becomes desirable or necessary to remove at least some of the above boiling aldehyde condensation by-products as shown e.g. in U.S. Patent Nos. 4,148,430 and 4,247,486. In such a case, it is desirable that the phosphorus ligand present (preferably in excess) exhibits a lower vapor pressure (higher boiling point) than the aldehyde condensation by-products, so that the ligand is not lost or depleted during the removal of the aldehyde condensation by-products. For example The volatility is related to the molecular weight and is inversely proportional to the molecular weight in the homologous series. Accordingly, it is preferable to use a diorganophosphite ligand, the molecular weight of which exceeds that of the trimeric aldehyde by-product corresponding to the aldehyde produced. And so e.g. Since the molecular weight of the trimeric pentanal is around 258 (C15H30O3) and the molecular weight of all the preferred diorganophosphites used in the process of the invention is greater than 330, it is clear that these diorganophosphites are particularly suitable for use in the hydroformylation or butene-1 and / or 2, as there should be no significant loss of the diorganophosphite ligand during the removal of the aldehyde formed and the above-boiling aldehyde by-product, which, as can be predicted in advance, would occur if a different lower molecular weight diorganophosphite ligand (e.g. higher vapor pressure or lower boiling point) than the molecular weight of the higher boiling aldehyde by-product. In addition, it would require the introduction of an additional processing stage if it was necessary to recover or reuse the phosphorus ligand. Although triorganophosphite ligands in general provide the formation of metal complex catalysts with sufficient activity to carry out the internal olefin hydroformylation reaction, experience has shown that their use, especially in a continuous hydroformylation process, can be judged as less satisfactory. This disadvantage associated with the use of trioorganophosphites has, as is recognized, their very high susceptibility to react with aldehydes, and the product formed is easily hydrotreated to the corresponding hydroxyalkylphosphonic acid, as shown in the diagram. Moreover, the formation of such acid is an autocatalytic process. This makes the triorganophosphite ligand even more susceptible to the production of such undesirable acid by-products, especially during rhodium-catalyzed hydroformylation with continuous recycle whereby contact between the phosphite ligand and the product aldehyde is prolonged. It has surprisingly been found that the diorganophosphite ligands used in the process of the invention are generally less sensitive to moisture and less reactive in the formation of this type of phosphonic acid than conventional triorganophosphites, thereby improving the stability and activity of the rhodium catalyzed hydroformylation process. continuously with recycle compared to the use of triorganophosphite ligands. It cannot be said, however, that during the continuous rhodium-catalyzed recycle hydroformylation process of the present invention, no hydroxyalkylphosphonic acid byproduct is formed. However, the build-up of undesirable hydroxyalkylphosphonic acid in the continuous recycle hydroformylation process of the present invention occurs at a slower rate than when using triorganophosphite ligands. This allows a longer and more efficient continuous process. And so e.g. , rapid decomposition of the phosphite ligand may not only adversely affect the activity and / or stability of the catalyst, but obviously leads to the rapid loss of the phosphite ligand, which has to be replaced with a ready-to-use phosphite ligand, and also promotes the further autocatalytic formation of unsatisfied hydroxyalkylic acid. which is often insoluble in the liquid medium of the hydroformylation reaction. Consequently, the rapid and abundant formation of this hydroxyalkylphosphonic acid can lead to its precipitation as an obviously undesirable, jelly-like by-product that may clog and / or contaminate the lines of the continuous process system in the liquid phase, thus necessitating periodic pauses or breaks for the removal or destruction by an appropriate method, e.g. using extraction with a weak base such as sodium bicarbonate. Moreover, it has surprisingly been found that the above-mentioned disadvantages of a by-product of this type, namely hydroxyalkylphosphonic acid, can be efficiently and advantageously limited by passing a liquid-phase effluent stream through a continuous recycle process, or before or more preferably after separation. the aldehyde produced, by means of a suitable weakly basic ammonite resin, such as amine-Amberlyst * resin, e.g. Amberlyst ^ A-21 etc. to remove some or all of the undesirable by-product hydroxyalkylphosphonic acid that might be present in the catalyst-containing liquid stream prior to its reintroduction into the hydroformylation reactor. Of course, if desired, more than one such base of basic ammonite resin may be used, e.g. a variety of such deposits, and each such deposit can be readily removed and / or replaced as necessary or desired. Alternatively, if desired, all or any portion of the catalyst-containing recycle stream contaminated with hydroxyalkylphosphonic acid may be periodically removed from the continuous recycle operation and the contaminated liquid thus obtained treated in the same manner. a method as generally described above to remove or reduce the amount of hydroxyalkylphosphonic acid contained therein prior to reusing the catalyst-containing liquid in the hydroformylation process. Likewise, any other method of removal of this type of by-product may be used here, namely hydroxyalkylphosphonic acid from the hydroformylation process of the present invention, if another method is desired. Accordingly, another advantageous and novel aspect of the present invention relates to an improved continuous hydroformylation process to produce aldehydes wherein an olefinic compound is reacted with carbon monoxide and hydrogen in the presence of a liquid environment containing a dissolved rhodium-organophosphite complex catalyst, solvent Nickel, free organophosphite ligand and aldehyde as a reaction product, the improvement consisting in minimizing the decomposition of free organophosphite ligand by a / removing the stream of said liquid medium from the hydroformylation reaction zone, b / dividing the so-removed environment into a slightly alkaline liquid the ammonite resin, and c) return of the treated liquid medium to the hydroformylation reaction zone. This type of treatment of a liquid medium with a weakly basic ammonite resin involves passing the liquid medium, that is, the effluent stream of the liquid reaction medium, after removal of said stream from the hydroformylation reaction zone, either before and / or after separation of the product aldehyde therefrom through a basic bed. ammonite resin. The method may use any suitable weakly basic ammonite resin. The weakly basic ammonite resins which can be used in the process of the invention as indicated by way of illustration may include third-order cross-linked resins. an amine polystyrene ammonite resin of the gel or macroretical type, e.g. amino-Amberlyst® resin, and more preferably Amberlyst® A-21, having a cross-linked polyester backbone with lateral benzodimethylamine [-CeH4-CH2-N / CHa / 2] functional groups. These types of weakly basic ammonite resin beds and / or methods for their preparation are well known in the art. 150 429 17 As noted above, the decomposition of the organophosphite ligand can be effectively limited and minimized by a preferred embodiment of the method according to the invention, which involves removing some or all of the undesirable hydroxyalkylphosphonic acid by-product that might be present in the liquid reaction environment as a result of the formation of itself in situ during the hydroformylation reaction and which is a substance that is autocatalytically formed when decomposing organophosphite, e.g. by side reactions of the phosphite ligand and the produced aldehyde. Since the small amounts of such hydroxyalkylphosphonic acids present in the hydroformylation reaction environment are difficult to determine by standard analytical methods such as gas chromatography or liquid chromatography, and as a result, in part, show high boiling point and polar nature, they have been used successfully 31PNMR (nuclear magnetic resonance) methods to detect even such small amounts of these acids as about 100 ppm by weight. And so e.g. , it may only be necessary to determine the detectable resonance peak (chemical shift in ppm relative to the external H3PO4) method 31PNMR for a synthetic comparative solution containing 100 ppm hydroxyalkyl sulfonic acid, and then control the hydroformylation reaction environment in the resonance process in the process in question same acid 31P NMR method. Thus, while the improvement in question generally includes a method of removing hydroxyalkylphosphonic acid from the liquid environment of the hydroformylation reaction, which already contains more than just trace amounts of this acid, to thereby minimize further degradation of the organophosphite ligand, experience has shown, however, that a very low-phosphoryl organophosphite ligand can decompose. when it is allowed to build up the amount of hydroxyalkylphosphonic acid above the trace amount. Thus, a preferred embodiment of the process according to the invention is that a treatment as above is directed to a reaction medium that does not even contain an easily detectable amount of this hydroxyalkylphosphonic acid, and that the treatment is started with the reaction medium before the build-up of the amount in question has even taken place. acid at an easily detectable level, such as 100 ppm by weight as determined by the 31PNMR method, so as to remove said hydroxyalkylphosphonic acid during its formation. Accordingly, while the invention encompasses both occasional and continuous treatment of the liquid reaction medium to minimize decomposition of the organophosphorine ligand, it is preferable to continuously work up the liquid reaction medium during the hydroformylation reaction. Moreover, the minimization of the degree of decomposition of the organophosphite ligand obtainable by the method of the invention can, if desired, be easily observed and quantified by determining, for a given process, the amount of organophosphite ligand remaining and / or lost in the environment of this hydroformylation reaction. the amount that was initially used, after a certain duration of the continuous hydroformylation process, compared with the amount of organophosphite ligand remaining and / or lost in the corresponding hydroformylation process under the same conditions but without treatment with a weakly basic resin ammonite as generally described in the above section of this specification. Accordingly, minimizing the degree of decomposition of the organophosphite ligand by preventing and / or slowing the reaction between such ligands and the aldehyde product allows a continuous process to be carried out longer and more efficiently than is the case with the comparative hydroformylation treatment carried out with hydroformylation. using a weakly basic anion exchange resin. Besides, in addition to preventing and / or minimizing the loss of ligand and produced aldehyde, the process of the present invention can also help to maintain a desired ratio of hydroformylation rate to aldehyde formation over an extended period of time, and to maintain the activity and / or stability of the catalyst, for which may be adversely affected by the rapid degradation of the organophosphite ligand. Further, the method according to the invention makes it possible to overcome the disadvantage of a rapid and profuse build-up of the above-mentioned hydroxyalkylphosphonic acid, leading to the precipitation of this acid in the form of an obviously undesirable gelatinous by-product which may clog and / or contaminate the lines of the hydroformylation process system. . The use of a weakly basic anion exchanger resin in the process according to the invention is indeed unique and surprising, since resins of this type, such as e.g. Amberlyst® A-21 are known to be highly reactive towards carboxylic acids, which are also secondary by-products of oxo reactions. This property alone would imply that the use of such resins would not be a practical means of removing phosphonic acid from the hydroformylation reaction medium stream as it would suggest that the acid neutralizing ability of the resin would be consumed too quickly by the carboxylic acid formed during hydroformylation. However, it has surprisingly been found that the neutralized carboxylic acid form of the Amberlyst® A-21 resin still remains basic enough to remove the stronger hydroxyalkylphosphonic acid from the hydroformylation liquid stream, even in the presence of carboxylic acids. Moreover, experience has shown that adding tertiary amines such as dimethylaniline, triethanolamine, proton sponge etc. to the phosphite ligand. promoted the rapid deposition of rhodium from the complex rhodium hydroformylation catalysts in the form of a black solid. Likewise, it has been found that Amberlyst® A-21 resin itself, when added to the hydroformylation reaction medium under hydroformylation conditions, causes precipitation of rhodium on the surface and pores of the resin. The most unexpected and successful thesis was that the use of a weakly basic anion exchange resin as described in the above section of this specification, such as e.g. Amberlyst® A-21, for treating the liquid stream of the reaction medium removed from the hydroformylation reaction zone, does not deleteriously precipitate rhodium or have an unduly detrimental effect on the rhodium catalyst and process in any clearly detrimental sense, e.g. by increasing the rate of formation of aldehyde by-products. It should be noted, however, that technically pure weak basic ammonite resins, such as Amberlyst® A-21, may contain halide impurities such as chloride, which are known to poison (adversely affect) complex rhodium hydroformylation catalysts. Thus, preferably, the weakly basic ammonite resins usable in the process of the invention are at least substantially free of halogen impurities, and more preferably should be essentially or completely free of such impurities. Removal of such halogenated impurities, as well as removal of any other undesirable impurities from this weakly basic anion exchanger resin prior to use, can be easily accomplished using conventional washing methods that are well known in the art. As noted hereinafter, the treatment of the liquid environment containing the dissolved rhodium-organophosphite complex catalyst, solvent, free organophosphite ligand, and product aldehyde must take place outside the hydroformylation reaction zone in a continuous hydroformylation process and the environment should be treated as such. be recycled to the hydroformylation reactor. Accordingly, this type of treatment is adaptable to the well known continuous gas and / or liquid recycle hydroformylation processes. And so e.g. , in a continuous gas recycle hydroformylation process, this treatment according to the invention may be carried out with occasional or continuous pumping, e.g. the effluent stream of the liquid reaction mixture from the reactor, followed by passing it through a bed of a weakly basic anion exchanger resin and recycling the liquid reaction mixture stream thus treated to the reactor. In the case of a recycle hydroformylation process, the liquid medium withdrawn from the reactor may be passed through the bed of weakly basic anion exchange resin at any point in the recycle process. For example In the case of the hydroformylation recycle method, the normal task is to continuously remove part of the liquid reaction medium from the reactor and the desired product aldehyde is recovered in one or more distillation stages, e.g. by passing said liquid environment to a vaporizer / separator, where the desired product is distilled and separated from said environment and possibly liquefied and recovered. The liquid residue obtained after the separation of the aldehyde so produced, the residue containing the rhodium-organophosphorin catalyst, solvent, free organophosphite ligand, and a certain amount of undistilled aldehyde product, is then returned to the reactor together with any slaughter products. such as e.g. hydroxyalkylphosphonic acid, which could also be present in said recycle residue. Although the treatment of such liquid reaction mediums from such continuous recycle hydroformylation processes may be carried out in the process of the invention either prior to and / or after isolation of the product aldehyde from this environment, it is preferably carried out with the process of the invention after removal or isolating the aldehyde produced. And so e.g. preferably, the weakly basic ammonite resin bed is located after the product aldehyde vaporizer / separator such that what passes through the weakly basic ammonite resin is the liquid recycle residue containing the catalyst, as explained above in this specification. In addition to being more convenient and economical in a system using this type of weakly basic ammonite resin bed, it is assumed that this location minimizes the amount of hydride of the rhodium catalyst that is to come into contact with the weakly basic ammonite resin, and the hydride form of the catalyst ancestral is considered a reactive form, which in the presence of e.g. The amines form insoluble anionic rhodium aggregates. It is believed that the hydride form of the rhodium catalyst, as it passes through the recovery stage of the aldehyde product by distillation, e.g. by the vaporizer / separator, in the hydroformylation process, it changes to the less active non-hydride form and that this less active form of rhodium catalyst is less able to complicate the process when it comes into contact with a weakly basic ammonite resin. In view of the fact that the treatment with a weakly basic ammonite resin within the scope of the present invention is intended to achieve the desired improvement, at least minimizing the degree of degradation of the organophosphite ligand used in the hydroformylation process to an extent that exceeds the results obtained in experiments. In the absence of such a resin treatment, it is evident that particular values cannot be arbitrarily given for such process conditions as the design, amount and position of the resin bed in the process system, as well as the temperature and contact time during the treatment. These conditions are not too narrowly critical and of course should only be at least sufficient to obtain the desired improvement. And so e.g. The method of the invention envisages the use of any conventional anion exchange resin bed structure through which a liquid environment to be treated may pass, each such deposit being readily removable and / or replaced if desired. Moreover, the number of the deposits used, as well as their location in the reaction system, are also not, as is believed, absolutely decisive and should only be such that they are appropriate to obtain the desired results. Likewise, the processing conditions, such as temperature, pressure, and contact time, can also be varied widely, depending on the wishes of the operator. Any suitable combination of these conditions may be taken for the method according to the invention, as long as the desired machining efficiency is achieved. Likewise, the treatment is preferably carried out under the normal working pressure of the system used, although, if desired, higher or lower pressures may be used, while the contact time of the warm environment passing through the resin bed is only seconds. Of course, it should be understood that while the selection of the appropriate optimal levels and conditions for the variables discussed in the above section of this specification depends on the experience of treating the resin with the method of the invention, it is only necessary to establish the conditions that are optimal in a given situation. little scope for experimentation. And so e.g. since the preferred embodiment of the method according to the invention is a continuous hydroformylation process in which, as long as possible, the decomposition of the organophosphite ligand used is prevented and / or minimized, and since this decomposition is believed to be accelerated by accumulation of an undesirable by-product in the form of hydroxyalkylphosphonic acid, it is obviously advantageous to successfully place the treatment with a weak base anion exchange resin bed at the start of the hydroformylation process used, or shortly thereafter, so that the liquid reacted environment can be reacted. continuously passing through the resin bed thereby preventing any excessive build-up of an undesirable acid by-product as discussed above in this specification. Of course, if desired, the resin can still be used in the process to readily remove detectable amounts of this type of hydroxyalkylphosphonic acid by-product that has accumulated, although it is a less desirable way to minimize the organophosphate ligand ligand component. In addition, the diorganophosphite ligands which can be used according to the invention have the additional advantage of showing an improved storage stability or shelf life compared to conventional triorganophosphites, such as monkylphosphites, e.g. trimethylphosphite, triethylphosphite etc, and triarylphosphite, e.g. triphenylphosphite, tris / 2-biphenyl / phosphite etc, especially in terms of moisture sensitivity and hydrolytic stability. The thesis should be clear that one of the presented advantages of using the diorganophosphite ligands according to the invention is, in contrast to the ligands used in the prior art, a high processing tolerance, as presented in the above part of this description, which is available when selecting the appropriate combination conditions that are most useful when it comes to achieving, or at least getting closer to, specific given results or needs. So, while it is clear that the process of the invention for rhodium hydroformylation represents a significant technical advance in the art, it should be noted that in the continuous recycle hydroformylation process of the invention, certain losses of rhodium, namely loss of rhodium from solution. It is believed that such rhodium losses were caused by the use of high temperature during the isolation of the desired rhodium-containing aldehyde from the resulting rhodium catalyst-containing solution, and that such rhodium losses can be reduced, even if not completely eliminated, by an isolation operation a desired aldehyde product from the resulting rhodium catalyst-containing solution under reduced pressure and low temperature, such as a temperature of less than 130 ° C, more preferably less than 110 ° C. In addition to providing basic advantages with respect to the activity and stability of the catalyst in the hydroformylation of olefin compounds to aldehydes as generally outlined above, it is believed that the diorganophosphite ligands of general formulas 2 and 5 as defined above, as well as complex rhodium catalysts containing these ligands The diorganophosphite formulas 2 and S defined above are new chemical compounds that are uniquely advantageous due to the fact that they can make it possible to use in a continuous hydroformylation process with recycle according to the invention, a higher temperature of evaporation (evolution) of the aldehyde than the temperature measured too favorable in the prior art. For example as noted above, in some experimental continuous recycle hydroformylation processes, some rhodium losses were experimentally found, and these losses were related in part to the evaporation temperature used in the isolation of the target aldehyde product from the final rhodium catalyst-containing solution. Accordingly, it has hitherto been advised to carry out such an aldehyde separation preferably at a temperature below 110 ° C in order to avoid such rhodium losses. It has now surprisingly been found that the release of the desired product aldehyde can advantageously be carried out at a temperature even higher, such as a temperature not higher than 120 ° C and possibly even higher when using the diorganophosphite ligand of the formula II or S, as proved by experiment. in which no losses of rhodium were observed, and over a longer period, in the hydroformylation reaction conditions carried out continuously at such a higher preferred temperature of evaporation (evolution) of the aldehyde and using [3.3 H-di-III-order. butyl-5-5'-dimethoxy-1-[alpha] -biphenyl-2-2'-diyl] phosphite. Of course, by itself, the benefits of a continuous process in which rhodium loss is prevented or at least minimized over a long period of time and associated with the possibility of using a higher temperature to separate the target aldehyde product from the reaction solution are evident. containing the catalyst without the associated drawback of rhodium losses. The higher the temperature taken in the evolution of the aldehyde, the more aldehyde produced - can be recovered for a given unit of time. In turn, the ability to extract more aldehyde product at a higher speed allows for better control of the process as regards the accumulation of higher-boiling aldehyde condensation by-products during the hydroformylation reaction, thus eliminating and / or minimizing any harmful build-up of this type. above boiling aldehyde condensation by-products. In addition, it is assumed that the diorganophosphite ligands of the formulas 2 and 5 as defined above, and the complex rhodium catalysts containing such ligands, are more easily soluble in the hydroformylation reaction environment than the corresponding diorganophosphite compounds of the same type, in which the formula Z2 and Zegl3 are hydrocarbon radicals , such as e.g. group Ill-rzed. butyl, and not ether radicals (i.e. oxyl), such as a hydroxy group and / or a group of the formula -OR as defined above in relation to formulas 2 and 5. Without being bound by any theory and without entering into any mechanistic disputes, it can be said that the solubility of Uganda may be the reason for the fact that for a long time no rhodium loss is observed at the temperature of aldehyde release higher than the temperature previously recommended as advantageous when [ 3.3'KU-III-row. butyl-5.5'Kta Alternatively, the complex rhodium catalysts containing ligand as defined in the aforementioned formulas 2 and 5 may undergo a structural change under the conditions of the hydroformylation and / or vaporizer / separator reaction to form a more stable or soluble rhodium complex by the presence of ether (i.e. oxyl) radicals represented by the symbols Z2 and Z3 in the formulas 2 and 5 defined above. Furthermore, while the diorganophosphite ligands of Formulas 2 and 5 as defined above, and the complex rhodium catalysts containing the diorganophosphite ligand are considered new chemicals, it should be understood that such ligands and catalysts can be easily prepared by the same general methods disclosed herein. in the description relating to the production of diorganophosphite ligands and complex rhodium catalysts in general. Likewise, diorganophosphites, in which the symbols Z2 and Z3 represent hydroxyl radicals, can be easily prepared by first obtaining the corresponding ligand in which the formula Z2 and Z3 represent an alkoxy radical, such as a benzyloxy group, and then carrying out the reaction dealkylation by any conventional method such as hydrogenolysis. The aldehydes obtained by the process of the invention are widely used and are particularly useful as starting compounds for the production of alcohols and acids. The invention is illustrated by the following examples. All parts, percentages, and shares are weighted unless otherwise stated. Example I. A wide variety of rhodium complex catalytic precursor solutions have been prepared, consisting essentially of dissolved rhodium-carbonyl-diorganophosphite-diorganophosphite-acetylacetonate complex catalytic precursor, organic solvent, and free diorganophosphite ligand and used for trans-butyl trans-butylformylation. aldehydes containing 5 carbon atoms in the molecule as follows. Dicarbonylodine acetylacetonate is mixed with a sufficient amount of ligand of 1'r-biphenyl ^^^ iyl- ^ i-di-III-order. butylmethylphenylphosphite of formula 29, the amount of ligand varying in each case as shown in Table 1 below, and then diluted with a sufficient amount of solvent (Texanol, 1,3-methylpentanediol monoisobutyrate) ), resulting in various rhodium catalytic precursor solutions containing rhodium and ligand in the amounts shown in the following table 1. Each of the aqueous catalytic precursor solutions thus produced was then used to hydroformylate the trans-butene-2 in 100 ml in a stainless steel autoclave equipped with a magnetic stirrer and connected to a gas manifold for the introduction of gases to the desired molecular pressure. The autoclave is also equipped with a pressure calibrator for determining the pressure during the reaction with an accuracy of ± 6.87 * 103Pa and a platinum resistance thermometer for determining the temperature of the solution 22 150 429 in the reactor with an accuracy of ± 0.1 ° C. The reactor is heated externally with two 300 W heating strips. The temperature of the solution in the reactor is regulated by using a platinum resistance sensor connected to an external proportional temperature controller to control the temperature of the external strip heaters. For each hydroformylation reaction, about 20 ml of a rhodium catalytic precursor solution prepared as above containing a rhodium complex, diorganophosphite ligand and solvent is introduced into the pressure reactor, and the solution is heated to the assumed reaction temperature as shown in the table below. 1. The pressure in the reactor is then reduced to 34.35 · 103 Pa and 5 ml (2.9 g) of trans-butene-2 are introduced into the reactor. Carbon monoxide and hydrogen (see partial pressures in Table 1 below) are then introduced into the reactor via a gas manifold and trans-butene-2 is hydroformylated under these conditions. The hydroformylation reaction rate in moles of aldehydes with 5 carbon atoms in the molecule / liter / hour is determined on the basis of sequential 34.35 * 103Pa pressure drops in the reactor, measuring the nominal operating pressure in the reactor, while the molar ratio of the compound produced is The straight chain (n-pentanal) is measured by gas chromatography to the resulting branched chain compound (2-methylbutanal). The results obtained are given in Table 1, with the said results being established after the conversion of the starting compound, trans-butene-2, of approximately 5-20%. Table 1 Gray No. ~ 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Temperature ° C 2 100 100 100 100 100 100 100 100 100 100 100 100 100 70 130 Rh ppm 3 25 50 250 500 250 250 250 250 250 250 250 250 250 250 250 Ratio. molar Ugand /, rhodium 4 10 10 10 10 3 9 18 10 10 10 10 10 10 10 10 Partial pressure • 103Pa H2 5 206.10 206.10 206.10 206.10 206.10 206.10 206.10 206, 10 206.10 206.10 103.05 412.20 618.30 206.10 206.10 CO 6 206.10 206.10 206.10 206.10 206.10 206.10 206.10 103.05 412, 20 618.30 206.10 206.10 206.10 206.10 206.10 Trans butene-2 mmole 7 50 50 50 50 50 50 50 50 50 50 50 50 50, 50 50 Reaction rate mol / liter / hour 8 2 , 94 5.73 4.63 4.95 17.19 5.73 2.96 3.78 6.68 7.76 3.55 7.29 7.93 0.64 12.85 Molar ratio of C5-aldehyde with straight chain / branched chain aldehyde 9 0.68 0.71 0.77 0.86 0.75 0.79 0.76 1.0 0.76 0.83 1.01 0.82 0.78 0.24 1.13 Ex. The process is carried out in the same manner and under the same conditions as in Example I for the preparation of the rhodium catalytic precursor solution using dicarbonylodine acetylacetonate, Texanol® and 1,1'-biphenyl-2,2'-diyl- (2-6-) ligand di- III-row. butyl-4-methylphenyl / phosphite and for the hydroformylation of trans-butene-2, except that the hydroformylation is applied instead of trans-butene-2 butene-1, instead of 20 ml of rhodium precursor solution, about 15 ml are used and the precursor solutions are changed catalyst containing the rhodium complex and the hydroformylation reaction conditions as shown in Table 2 below. The rate of the hydroformylation reaction is expressed in moles of aldehydes containing 5 carbon atoms in the molecule / liter / hour, and the molar ratio of the produced straight-chain compound (n-pentanal) to the produced branched-chain compound (2-methylbutanal) is the same method as described in the above example I. The results obtained are given in Table 2. 150 429 23 Gray No. 1 2 3 4 5 6 Temperature ° C 100 100 50 70 100 120 Rh ppm 200 200 250 50 25 50 Ratio. molar Ugand /. rhodium 10 10 5 10 5 20 Tabe Partial pressure HfPft H2 137.40 412.20 412.20 206.10 206.10 206.10 CO 137.40 412.20 412.20 206.10 206.10 206.10 la 2 Butene-1 millimoles 50 50 50 50 50 50 Reaction rate mol / liter / hour 0, * 8 14.5 242 2.37 1.23 3.41 The molar ratio of Cs-aMtfayd straight lance m 2 »V \ 2.48 1.51 1.14 Example III. The process is carried out in the same manner and under the same conditions as in Example I for the preparation of the rhodium catalytic precursor solution using dicarbonylene acetylacetonate, Texanol * and the ligand in the form of 1, r-biphenyl-2t2'-diyl- / 296-di-III. -before butyl-4-methylphenyl / phosphite and for the hydroformylation of trans-butene-2, with the exceptions that different organophosphite ligands are used, and the rhodium complex catalytic precursor solutions and the hydroformylation reaction conditions are changed as shown in Table 3. The rate of the hydroformylation reaction is expressed in moles of produced aldehydes containing 5 carbon atoms in the molecule (pentanals) / liter / hour, and the molar ratio of the produced straight-chain compound (n-pentanal) to the produced split-chain compound (2-methylbutanal) is described in this way. the above example I. The results obtained are given in Table 3. Gray No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Ligand / g / pattern 73 pattern 74 pattern 75 pattern 76 pattern 34 pattern 35 pattern 36 pattern 37 pattern 77 pattern 78 pattern 79 pattern 41 pattern 81 pattern 30 pattern 42 formula 43 Table Precursor solution and reaction conditions / b / / b / / b / / b / / c / / c / / c / / c / / a / / e, f / / e, f / / e / / e, f / d / / d / / d / 3 Reaction rate mol / liter / hour 4.7 3.4 / h / 17.82 / i / 0.46 U / j / 2.9 / j / 2 , 6 / j / 8.1 4.5 5.4 0.65 0.51 0.92 8.7 4.0 7.6 Mole ratio straight-chain / branched-chain aldehyde 0.7 0.89 0, 86 0.56 1.0 1.0 1.0 0.73 1.12 0.68 0.68 0.62 0.67 0.82 0.88 1.1 In the table 3 above, the following symbols were used: (a ) Precursor solution and reaction conditions: rhodium: 200ppm, diorganophosphite ligand: 6 moles / mole of rhodium, reaction temperature: 100 ° C, partial pressure Hgr 1.37 * CO: 1.37 • 105Pa, trans-butene-2: 50 millimoles . (b) Precursor solution and reaction conditions: rhodium: 200ppm, diorganophosphite ligand: 10mol / mole of rhodium, reaction temperature: 105 ° C, partial pressure H *: 2.06 'CO: 2.06 • 105 Pa, trans-butene- 2:50 millimoles. (c) Precursor solution and reaction conditions: rhodium: 230ppm, diorganophosphite ligand: 3mol / mol of rhodium, reaction temperature: 100 ° C, H2 partial pressure: 1.37 <105Pa, 10 * Pa, CO: 1.37-10 ° solution. 10 * Pa, Pa, trans-butene-2: 50 mmol. Instead of 20 ml of rhodium catalytic precursor solution, use 15 ml of this 24 150 429 (d) Precursor solution and reaction conditions: rhodium: 200 ppm, diorganophosphite ligand: 10 mol / mol of rhodium, reaction temperature: 105 ° C, H2 partial pressure: 2.06 • 105Pa , CO: 2.06-10 * Pa, trans-butene-2: 50 mmol. Instead of 20 ml of rhodium catalytic precursor solution, 15 ml of this solution is used. (e) Precursor solution and reaction conditions: rhodium: 200ppm, diorganophosphite ligand: 6mol / mole of rhodium, reaction temperature: 100 ° C, H2 partial pressure: 1.37-105Pa, CO: 1.37 * 105Pa, trans-butene- 2: 50 millimoles. 15ml of this solution is used instead of 20ml of rhodium catalytic precursor solution. (F) RI14 / CO / 12 is used instead of dicarbonylodine acetylacetonate as the rhodium precursor. (g) BHT - 2,6 Kli-IfI-tert.butyl-4-triethylphenyl (in the formulas) :; -Bu - rhodiiik IH-rzcd.butyl.Ph - phenyl (h) The activity of this comparative triorganophosphite activator catalyst declines rapidly during continuous hydroformitation (see example V below). (i) The activity of this diorganophosphite activator catalyst decays very quickly during a continuous experiment in a glass reactor similar to that described in Example 5 below. (j) The activity of these catalysts with the addition of diorganophosphite as activator is very severely inhibited when the ligand is used in amounts greater than 3 molar equivalents / mol of rhodium. Example IV. The process is carried out in the same manner and under the same conditions as in Example I for the preparation of a rhodium catalytic precursor solution using dicarbonylene acetylacetonate, Texanol®, and the 19l, -biphenyl-292, -diyl- (2,6-di-) ligand Tertiary butyl-4-methylphenyl / phosphite and for the hydroformylation of trans-butene-2, with the exceptions that various, different olefin compounds are used as starting compounds for the hydroformylation reaction and the precursor catalytic solutions containing the rhodium complex are changed. and the hydroformylation reaction conditions as shown in Table 4 below. The rate of the hydroformylation reaction, expressed as moles of aldehyde produced / liter / hour, as well as the molar ratio of straight chain aldehyde produced to produced branched aldehyde, is determined by the method described in the above example I. The results obtained are given in Table 4: Olefin compound 1 Butene-1 Butene-2 (trans) Isobutene Cyclohexene Dicyclopentadiene Vinyl acetate Allyl alcohol Allyl tertiary butyl ether Hexadiene-1,5 Ethylene Ethylene Propylene Cyclohexene Decene-1 Styrene Methyl methacrylate [Rh] ppm 2 200 250 150 150 150 200 100 100 100 100 500 500 200 200 200 200 Molar ligand / rhodium ratio 3 10 10 10 10 10 10 10 10 10 10 3 3 25 20 10 10 Table 4 Partial pressure every 4 412.20 206.10 103.05 412.20 412.20 412.20 412.20 412.20 412.20 137.40 171.75 171.75 274.80 326.32 326.32 326.32 • 103 Pa H2 5 412.20 206.10 309.15 412.20 412.20 412.20 412.20 412.20 412.20 137.40 171.75 171.75 274.80 326.32 326.32 326.32 Olefin compound * 7 6 50 50 50 63 9.2 54 73 , 5 30 43/171/75 / / 171.75 / / 171.75 / 50 22 30 47 Temperature ° C 7 100 100 115 100 100 80 70 70 70 60 30 30 160 100 100 100 Reaction rate mol / liter / hour 8 14.5 4.63 1.65 4.8 2.1 0.37 2.97 1.90 2.11 1.48 0.27 0.14 3.5 5.7 10.0 2.5 Ratio straight chain aldehyde / branched chain aldehyde 9 2.3 0.77 abcde 1.3 2.7 fgg 1.77 b 1.1 h 1.9 ij W po in table 4 above, the following notations were used: a Forms one product (3-methylbutanal). _b Creates one product (cyclohexanecarboxaldehyde). 150 429 25 c You create different isomeric aldehydes. d Only the branched-chain isomer, α-acetoxypropanal, is detected. e Detects only the straight-chain isomer, 4-hydroxybutanal. f Ratio refers to the ratio of hepten-6-alu-1 and 2-methylhexene-5-alu-1. g Creates one product (propanal). h The ratio relates to the ratio of n-undecanoate and 2-methyldecanal. and The ratio relates to the ratio of 3-phenylpropanal and 2-phenylpropanal. jTrzysie is the only one product (methyl / 2-methyl-J-phonyl / propanal). . _ '% / In the column: values without parentheses apply to roilimoles, and tcn values in brackets-l Example V. Long-term catalytic stability of rhodium catalyst with the addition of l ^ biphenylc-2,2'-diyl- / 2,6-di-III-i ^ new of example 1 as an activator, compared to the rhodium catalyst with the addition of diphenyl (2,6-di-tertiary-butyl-4-methylphenyl) phosphite (ligand triorganophosphite from gray No. 2 in table 3 above) is determined as follows These long-term catalytic stability experiments are carried out by hydroformylating trans-butene-2 in a glass reactor by a continuous single-pass method. The reactor consists of an 88.71 ml pressure cylinder immersed in an oil bath with a front training wall for viewing. In each experiment, about 203 ml of a freshly prepared rhodium catalytic precursor solution is introduced into the reactor after the entire system has been purged with nitrogen. Each such precursor solution contains about 200 ppm of rhodium, introduced as dicarbonylene acetylacetonate, about 5 molar equivalents of phosphorus ligand / mol of rhodium metal and a trimeric n-pentanal solvent. After closing the reactor, the system is purged with nitrogen again and the oil bath is heated to the temperature set for the hydroformylation reaction. In each experiment, the hydroformylation reactions are carried out at a total pressure of about 1.13-10 bar, a partial pressure of hydrogen about 206.10-103 Pa, trans-butene-2 about 164.88-103 Pa and carbon monoxide about 206.10-103. Pa (rest is nitrogen pressure). The flow of feed gases (carbon monoxide, hydrogen and propylene) is controlled separately for each of them by means of flowmeters, and the gases introduced into the reactor are dispersed in the precursor solution by means of a stainless steel beam. The unreacted part of the feed gases carries away the product aldehydes containing 5 carbon atoms in the molecule. The exhaust gas is analyzed for the presence of these aldehydes over a 4 day continuous process at the temperature shown in Table 5 below. This table also shows the average rate of reaction for each experiment, expressed as moles of aldehydes containing 5 carbon atoms in molecules / liter / hour as well as the molar ratio of n-pentanal to 2-methylbutanal for each day of the process Table 5 Test results - daily averages and ligand used 1 AA Process days 2 1.0 1.9 2.9 3.5 4 , 4 Temperature ° C 3 105 105 105 105 105 Rod ppm * 4 170 167 171 174 170 Ligand% wt 5 0.4 0.3 0.4 0.4 0.4 CO 6 212.97 206.10 206.10 206.10 199.23 Partial pressure -10 * Pa H2 7 206.10 199.23 199.23 212.97 212.97 Trans-butene-2 8 123.66 158.01 151.14 158.01 164.88 B 1.0 105 177 0.4 206.10 240.45 178.62 1.9 105 184 0.4 206.10 192.36 226.71 2.9 105 189 0.4 206.10 199.23 233 , 58 3.5 105 192 0.4 199.23 212.97 233.58 B 4.4 105 186 0.4 206.10 212.97 226.7115 * 429 Table 5 continued Use y Ugand AABB Process days 1.0 1.9 2.9 3.5 4.4 1.0 1.9 2.9 3.5 4.4 Reaction rate mol / liter / hour 0.83 1.09 1, 05 1.03 1.06 0.36 0.26 0.17 0.12 0.09 Straight chain aldehydes molar ratio to aldehydes with branched chain 1.05 1.08 1.09 1.12 Ul 0.74 0, 69 0.51 0.47 0.68 Butene-1 ** (mole%) 5.90 6.04 5.92 5.86 5.84 5 ^ 57 4.98 4.10 3.16 2JS6 In the above table The following 5 symbols were used: A U '^ ifenyk-2 ^^ ykH / 2.6 ^ -IU-rzcd B diphenyl / 2.6 ^ -in-raed.butylc-4-methylphenyl / phosphite. * Changing values reflect changes % of the daily average levels of solution in the reactor. ° Percentage of isomeric butene-1 in total butenes in the reactor outlet gas. The above data show that the ligand of diorganophosphite [l, r-biphenyl-2,2 / -diyl- / 2,6-di - III-xzcd.butyl-4-methyl-phenyl / phosphite] according to the invention over a period of four days of continuous hydroformylation, while the catalyst with the addition of the comparative triorganophosphite ligand [diphenyl The / 2.6 activator, which is not concerned by the present invention, loses about 75% of its catalytic activity at the same time. The analysis of the exhaust gas composition shows that complete (equilibrium) isomerization of the pure 2-butene introduced is achieved in this case when the diorganophosphite (ligand A) is used. The outlet concentration of 1-butene in the total amount of butenes at the outlet approaches the calculated thermodynamic equilibrium value of 5.77 mol% of 1-butene at 105 ° C and a total pressure of 1202-10 Pa. Triorganophosphite (ligand B) has the ability to isomerize butene-2, but this ability declines rapidly during the duration of the test. Example VI. A variety of rhodium complex precursor catalytic solutions have been prepared, consisting essentially of a rhodium carbonyl diorganophosphite-diorganophosphite-acetylacetonate complex catalytic precursor solution, an organic solvent, and free diorganophosphite ligand, and the alodium acetyl acetylated carboxylate is used to convert the alodium acetylated carboxylate. Sufficiently mixed with the triorganophosphite ligand, then the resulting mixture is diluted with sufficiently used Texanol® solvent to obtain a rhodium catalytic precursor solution containing about 150 ppm of rhodium based on free metal and about 10 equivalents molar diorganophosphite ligand / mole of rhodium. The type of ligand is varied as shown in Table 6 below. In each hydroformylation reaction, about 20 ml of the rhodium catalytic precursor solution thus prepared are introduced into the pressure reactor described in Example 1 above and heated to the reaction temperature used in the above-mentioned example. are given in Table 6 below. The pressure in the reactor is then brought to 6.87 × 103 Pa with nitrogen, and then 5 ml (about 3.12 g) of isobutylene are introduced into the reactor. Then, the synthesis gas in the form of a 1: 1 mixture of carbon monoxide under a pressure of 103.05 * 103 Pa is introduced into the reactor through a gas pipe, which is branched under a pressure of about 206.10-103 Pa. and hydrogen at a pressure of 103.05-103 Pa, and under these conditions isobutylene hydroformylation is carried out. The hydroformylation reaction rate in moles of aldehyde produced (the only aldehyde produced here is 3-methylbutanal) / liter / hour, is determined on the basis of sequences, 34 , 35-103 Pa, pressure drop in the reactor, measuring the nominal operating pressure in the reactor. 150 429 27 The results obtained are given in the following table 6, with the said results being established after conversion of the starting compound, isobutylene, to about 30%. 6 Gray ° * 1 1 2 3 4 5 6 7 8 9 10 U 12 13 14 15 16 17 18 19 20 21 22 Ligand 2 design 48 design 47 design 45 as above as above pattern 46 pattern 50 pattern 82 pattern 83 pattern 84 pattern 85 pattern 86 pattern 49 pattern 32 pattern 87 pattern 88 pattern 89 pattern 90 pattern 91 as above pattern 30 pattern 39 Temperature ° C 3 "115 ~ 115 115 100 85 100 100 100 100 100 100 100 100 100 100 100 100 100 100 115 100 100 Reaction rate mol / liter / hour 4 ¦ GflT 0.42 1.80 1.50 1.15 1.38 2.15 1.49 1.92 0.05 1.56 0.34 0.86 3.25 0.40 0.22 0.05 1.29 1.25 0.87 2, 99 3.30 The following notations are used in Table 6. In the formulas: t-Bu t -butyl radical.MC 1-methylcyclohexyl radical Example 7 A number of different rhodium complex-containing catalytic precursor solutions are prepared, consisting essentially of a precursor solution a catalytic rhodium-carbonyl-diorganophosphite-acetylacetonate complex, an organic solvent and a free diorganophosphite ligand, and uses for the hydroformylation of trans-butene-2 to aldehydes containing S carbon atoms in the molecule, thus liganding a diorganophosphite diorganophosphite ligand. amount, then the obtained mixture is diluted with the used in sufficient amount ro with a solvent, Texanol®, to obtain a rhodium catalytic precursor solution containing about 250 ppm of rhodium on a free metal basis and about 10 molar equivalents of diorganophosphite ligand / mole of rhodium. The type of ligand is varied as set forth in Table 7 below. In each hydroformylation reaction, about 15 ml of the so prepared rhodium catalytic precursor solution is introduced into the pressure reactor under nitrogen and heated to a hydroformylation reaction temperature of 100 ° C. The pressure in the reactor is then reduced to 34.35 * 103 Pa, and then 5 ml (2.9 g) of the olefin compound adopted for the experiment are introduced into the reactor, as shown in Table 7 below. gas pipeline branched under pressure about 618.30 * 103 Synthesis pagase in the form of a 1: 1 mixture of carbon monoxide under a pressure of 309.15 * 103 Pa and hydrogen under a pressure of 309.15 * 103 Pa and under these conditions the olefin compound is hydroformylated. hydroformylation reaction in moles of aldehydes produced with 5 carbon atoms per molecule / liter / hour is determined on the basis of sequential 34.35 * 103 Pa pressure drops in the reactor, measuring the nominal working pressure in the reactor, while the molar ratio of the produced straight-chain compound (n-pentanal) to the produced branched-chain compound (2-methylbutanal) is measured by gas chromatography. 150 429 28 The results obtained are given in Table 7 below, these results are determined after the conversion of the starting compound, trans-butene-2, is approximately 5-20%. Table 7 Gray No. 1 2 3 4 5 6 7 8 9 Ligand pattern 48 pattern 47 pattern 45 pattern 46 pattern 50 pattern 51 Formula 92 Formula 93 Formula 94 Reaction rate mol / liter / h 0.0 2.8 7.0 8.1 12.0 12.0 1.9 5.5 8.1 Molar ratio of straight chain aldehyde to lance aldehyde .g. - • • 0.72 0.62 0.67 0.78 0.93 1.2 0.67 0.69 The following notations were used in Table 7: In the formulas: t - Bu radical III-shoe order. Example VIII. The aldehyde activity of the various diorganophosphite and triorganophosphite ligands is determined as follows: A series of phosphite-aldehyde solutions are prepared, each in the same way, with up to 59.14 ml narrow-necked cylinders with a stirrer anchor. After drying in an oven at 150 ° C for an hour and then cooling it in a dry chamber to room temperature, about 4.5 millimoles of phosphite ligand, about 3.0 millimoles of triphenylphosphine oxide (as the phosphorus-containing internal standard) are successively introduced. and, sufficiently, a mixture of n-pentanal and 2-methylbutanal so as to obtain a total of 30 g of each solution. The bottles are then closed with a serum stopper, removed from the dry chamber and placed on a magnetic stirrer at ambient temperature until a solution is obtained. The bottles are then placed back in the dry chamber and kept under nitrogen at room temperature. From time to time, 3 ml of samples are taken from each solution and their phosphorus concentration is determined by the 31PNMR method. The size of the phosphite decomposition as a result of the reaction with the aldehyde is qualitatively determined by the relative intensity of the 31PNMR resonance corresponding to the intensity of the pure phosphite ligand and the internal standard used. Phosphite ligands used and the test results obtained are given in Table 8. Day 1 Day 4 Day 7 Day 10 1 2 3 4 5 6 pattern 95 pattern 96 pattern 97 pattern 34 pattern 98 pattern 29 A little bit None All A little None All Most Part - Most None Most None All None The following symbols are used in table 8: : t-Bu 111-butyl radical Ph phenyl radical Example IX. The high-temperature aldehyde activity of the various phosphite ligands is determined as follows: A series of phosphite-aldehyde solutions are prepared, each in the same way, with up to 354.84 ml Fischer-Porter bottles equipped with a stirrer anchor. magnetics-150 429 29 cc, about 0.005 moles of phosphite ligand, about 0.0075 moles of barium carbonate, about 0.0025 moles of barium valerate (barium salts are used to keep the solution neutral) and, in sufficient quantity, a mixture n-pentanal and 2-methylbutanal, so as to obtain a total of 100 g of each solution. The cylinders are closed with a pressure cap modified to contain a mechanical stirrer, gas flush valve and sampling valve and seat in a stainless steel mesh security case. The cylinders containing the phosphite-aldehyde solution are then purged with nitrogen and the nitrogen is kept in it under a pressure of about 343.50 • I03 Pa. Then each solution is stirred for an hour at ambient temperature, and then heated by placing the cylinder in a preheated cylinder 160 ° C silicone oil bath. Each solution is periodically sampled and the phosphite concentration determined quantitatively by liquid pressure chromatography. The phosphite ligands used and the dimensions of phosphite decomposition as a result of the reaction with the aldehyde are given in Table 9. Table 9 Szarz No. 1 2 3 4 5 6 Ugand formula 97 formula 29 formula 31 formula 73 formula 74 formula 80 ° C 160 160 160 160 160 160 Reaction time (h) 23.5 21 25 21 21 25 Decomposed ligand (%) 44 13 0 4 4 0.5 The following notations are used in Table 9: In the formulas: t-Bu t -butyl radical Ph phenyl radical Example X. Continuously, with the recycle of the catalyst-containing liquid, the olefin starting material, a mixture of butene-1 and butene-2 (cis and trans), is hydroformylated over six days, followed by hydroformylation of butene-1 continuously with the recycling of the liquid containing the catalyst as follows The set of recycle reactors used here consists of two 2.8 liter stirred tank reactors made of stainless steel connected in series with each of them equipped them st with a vertically mounted agitator and a ring-shaped tubular bubbler, close to the bottom of the reactor, intended for the introduction of the olefin compound and / or syngas. The bubbler has a number of openings of sufficient size to provide the desired flow of gas into the liquid. Reactor 1 is provided with a silicone oil jacket to bring the contents of the reactor up to the reaction temperature, while the reaction solution in reactor 2 is heated by an electric heater. Both the reactor and the second have an internal coil to control the reaction temperature. Reactor 1 is connected to reactor 2 by a line designed to transfer any unreacted gases from reactor 1 to reactor 2, and the reactors are connected to each other by a line so that a part of the liquid reaction solution containing the aldehyde product and catalyst can be pumped from reactor 1 to reactor 2 to subject unreacted olefinic compound from reactor 1 to further hydroformylation in reactor 2. Each reactor also includes a pneumatic liquid level regulator for automatic control of the liquid level in the reactor. Thereafter, reactor 1 is also provided with a line for introducing the olefin compound and synthesis gas through a bubbler, while the finished synthesis gas is introduced into reactor 2 through the same conveying line through which unreacted gases from reactor 1 are conveyed. Reactor 2 also contains exhaust vent to remove unreacted gases. A conduit from the bottom of reactor 2 is connected to the top of the vaporizer so that part of the reaction solution from reactor 2 can be pumped to the vaporizer. The evaporated aldehyde is freed from non-vaporized components of the reaction solution in the gas-liquid separator part of the vaporizer. The remaining, non-evaporated reaction solution containing the catalyst is pumped through the return line back to reactor 1. The return line is also provided with a pneumatic liquid level regulator. The product aldehyde evaporated is passed to the water-cooled cooler where it condenses and is collected in the product receiver. The hydroformylation reactions are carried out as follows. About 0.789 liters of the precursor catalytic solution containing dicarbonyl rhodium acetylacetonate (about 200 ppm of rhodium), about 1.0 wt.% Of the ligand in the form of 1, r-biphenyl-1-diyl-4-biphenyl-3-butyl-4, are introduced into reactor 1. -methylphenyl / phosphite (about 10 mole equivalents of ligand / mole of rhodium), about 0.5 wt% of 2,6-di-tertiary butyl 4-methylphenol as an antioxidant and about 98.5 wt% of an aldehyde with 5 carbon atoms in the molecule (about 68.5% by weight of pentanal and about 30% by weight of trimeric pentanal) as solvent. About 0.96 liters of the same catalytic precursor solution are fed to reactor 2. The reactor system is then purged with nitrogen to remove any oxygen present in the system. Nitrogen is then introduced into the reactors at a pressure of 687.00 * 103 Pa and the reactors are heated to the assumed reaction temperature given in Table 10 below: On the bottom of reactor 1, introduces through a bubbler, under a regulated flow, purified hydrogen, carbon monoxide and a mixture of olefinic starting compounds in the form of butene-1 and butene-2 (cis and trans) and increases the pressure in the reactor to the operating pressure given in the table below 10. When the liquid level in reactor 1 starts rise due to the formation of liquid aldehyde product of the reaction, then part of the reaction solution is pumped from reactor 1 to reactor 2 through the conduit leading to the top of reactor 2 at a rate sufficient to maintain a constant liquid level in reactor 1. The pressure in reactor 2 is increased to the value working pressure given in the table below 10. The amount is measured and the composition of the gas discharged from reactor 2 is tested. Ready-to-use synthesis gas (CO and H 2) is introduced into reactor 2 at a controlled flow in order to maintain the desired partial pressure of both components in reactor 2. The operating pressure and reaction temperature are kept constant during the hydroformylation reaction. When the liquid level in reactor 2 begins to rise due to the formation of the liquid aldehyde product of the reaction, part of the reaction solution is pumped to the vaporizer / separator at a rate sufficient to maintain a constant liquid level in reactor 2. The crude aldehyde produced is separated from of the reaction solution at a temperature of 115 ° C. and a pressure of 137.40 × 103 Pa, then condensed and collected in the product receiver. The remaining non-evaporated reaction solution containing the catalyst is recycled back to the reactor 1. The hydroformylation of said raw material in the form of an olefin mixture of butene-1 and butene-2 is carried out continuously for six days and after this time the olefin raw material is changed to the raw material with butene-1 predominating, and the reactions are continued for one more day. Conditions for the hydroformylation, as well as the rate of formation of aldehydes containing 5 carbon atoms in the molecule, expressed in moles / liter / hour, and the mole ratio of aldehyde products straight chain for branched chain aldehyde products (n-pentanal to 2-methylbutanal) are given in the table below 10.150 429 31 Table 10 Process days Feed butene,% mol Butene-1 Trans-butene-2 Cis-butene-2 Reactor No. 1 Temperature ° C Pressure * 103Pa H2-103Pa CO103Pa Butene-1103Pa Trans-butene-2 • 103Pa Cis-butene-2-103Pa Reactor no.2 Temperature ° C Pressure *] O3 Pa H2 * 103Pa CO103 Pa Butene-1-10 ^ Pa Trans-butene-2 • 103 Pa Cis-butene-2-103 Pa Results Cs-aldehydes, mol / liter / hour Molar ratio of straight-chain aldehydes to branched-chain aldehydes 2 5.22 57.00 37.78 85.2 1,408.35 592.88 437.62 * 4.81 158.01 50.151 85.1 1270.95 575.71 260.37 3.44 111.29 26.11 3.03 0.47 6 41.27 34.06 24.67 85.4 1408.35 441.05 443.49 10.31 127.10 48.78 85.5 1270.95 378.54 376.48 2 , 06 75.57 19.92 3.19 0.78 7 99.97 0.0 0.03 66.1 140 835 537.92 521.43 173.81 7.56 11.68 68.5 1270.95 373 , 73 357.24 48.09 14.43 19.24 3.19 2.44 Analysis of the rhodium complex catalyst solution following the completion of the above experiment on a continuous seven-day hydroformylation step shows that the catalyst solution used in The reaction contains about 173 ppm of rhodium. A comparative experiment is carried out using a method similar to that described in Example X above, except that the crude aldehyde produced separates from the reaction solution. in a vaporizer under conditions such as a temperature of about 87-89 ° C and a pressure of about 34.35-103 Pa, and a recycle catalyst solution is passed through an Amberlyst® A-21 resin bed to remove acid by-products. After an equilibrium period of one day, during which some rhodium is believed to be adsorbed onto the Amberlyst® resin, no detectable loss of rhodium contained in the reactor is detected in the next 10 days of continuous hydroformylation reaction. . A comparative continuous hydroformylation experiment similar to that set forth in Example X above was carried out using tris-ortho-biphenylphosphite (Gray No. 3 in Table 8 above, phosphite not covered by the present invention) as a catalyst activator ligand. . The process is followed as for the initiation of the process and the method of its operation according to the above example X, with the exception that in this test, instead of two reactors connected in series, only one reactor is used and the feed is butene-1 as the olefin compound. 0.88 liters of catalytic composition consisting of 100 ppm of rhodium in the form of dicarbonylene acetylacetonate, 10% by weight of tris-ortho-biphenylphosphite (about 192 molar equivalents of phosphite ligand / molar equivalent of rhodium) dissolved in a 1: 1 mixture are introduced into the reactor. / w / w / pentanal and Texanol®. At the end of 0.8 days of operation, a heavy precipitate of α-hydroxypentylphosphonic acid appears which causes clogging of the feed lines of the reactors and consequent disruption of the continuous hydroformylation. Analysis of the catalyst solution using the 31PNMR method shows that all the tris-ortho-biphenylphosphite is decomposed. The hydroformylation test is complete. The data in Table 11 refer to the process conditions and the results obtained. Table 11 1 Process days Butene feed,% mol Butene-1 Trans-butene-2 Cis-butene-2 Butane Reaction conditions Temperature ° C Pressure • 103 Pa H2, 103 Pa CO 103 Pa Butene-1 -103 Pa Results Cs-aldehydes, reaction rate / mol / liter / hour Straight chain to branched aldehyde molar ratio 2 0.8 99.2 0.2 0.05 0.55 80 , 3 1030.50 221.90 300.22 416.32 1.02 3.04 Example XII. The long-term catalytic stability of the rhodium catalyst with the addition of 1,3-biphenyl-2,2'-diyl- (2,6-di-tertiary b) as activator is determined as follows. Hydroformylation is carried out in a glass reactor in the manner continuous with a one-time pass. The process concerns the hydroformylation of propylene. The reactor consists of an 88.71 ml pressure cylinder immersed in an oil bath with a glass front wall for viewing. To the reactor, after purging the system with nitrogen, about 20 ml of a freshly prepared solution of rhodium catalytic precursor are introduced using a syringe. The precursor solution contains about 200 ppm of rhodium introduced as dicarbonylene acetylacetonate, about 10 molar equivalents of the ligand, 1,1-biphenyl-2,2'-diyl- (2,6-di-tert-butyl-4-methylphenyl) phosphite / mole of rhodium metal and Texanol® as solvent. After the reactor is closed, the system is purged with nitrogen again and the oil bath is heated to the temperature set for the hydroformylation reaction. The hydroformylation reactions are carried out at a total pressure of about 1099.20 bar, the partial pressures of hydrogen, carbon monoxide and propylene as shown in Table 12 below (the residual pressure is nitrogen and the aldehyde formed). The flow of feed gases (carbon monoxide, hydrogen, propylene and nitrogen) is controlled separately for each of them by means of flowmeters, and the gases entering the reactor are dispersed in the precursor solution by means of a sintered glass beam. The unreacted part of the feed gases carries away the formed aldehydes containing 4 carbon atoms in the molecule. The exhaust gas is analyzed over the 22-day duration of the reaction given in the following table 12. This table also shows the average reaction rate for each experiment in moles of aldehydes produced containing 4 carbon atoms in the molecule / - 'liter / hour, as well as the mole ratio of the produced n-butanal to isobutanal 150 429 33 Process days 0.6 1.4 2.6 3.9 4.9 4.5 6.7 7.7 7.1 9.6 11.0 12.0 12.6 13.7 14.7 15.6 16.9 17.9 18.9 19.6 22.5 Temperature ° G 73 91 91 91 91 91 91 91 91 91 91 91 91 89 88 101 91 91 91 91 92 Rod ppm X 132 159 145 135 126 136 173 179 188 198 197 197 197 209 209 214 199 200 202 204 209 Ligand wt% 0.7 0.8 0.7 0.7 0.6 0.7 0.9 0, 9 0.9 1.0 1.0 1.0 1.0 1.1 1.1 1.1 W 1.0 1.0 1.0 1.0 Table 12 Test results mean daily Partial pressure CO 144.27 254.19 226.71 281.67 267.93 261.06 274.80 281.67 288.54 288.54 281.67 144.27 281.67 199.23 281.67 288.54 274.80 281, 67 281.67 274.80 288.54 HfPa H2 247.32 343.50 288.54 364.11 343.50 343.50 350.37 364.11 4123 357, 54 343.50 583.95 343.50 535.86 343.50 343.50 343.50 343.50 343.50 343.50 343.50 Propylene 34.35 41.22 48.09 27.48 27.48 34.35 41.22 48.09 61.83 41.22 48.09 130.53 54.96 96.18 54.96 61.83 54.96 54.96 61.83 61.83 54.96 Speed of response mol / liter / hour 1.09 2.62 2.40 2.22 2.24 2.37 2 ^ 9 2.12 1.93 2.10 2.42 0.94 2.35 1.86 2.56 2.40 2.46 2.46 2.38 2.48 2.34 Molar ratio of linear aldehyde / branched aldehyde 0.86 1.02 1.01 1.04 1.01 1.04 1.08 1.03 0.90 1.06 1.07 036 1.06 0.77 1.09 1.05 1.08 1 , 07 1.07 1.07 1.08 The following notations are used in Table 12: x The changing values reflect changes in the daily average solution levels in the reactor. Example XIII. A continuous hydroformylation experiment, similar to that in Example X above, is performed using isobutylene as the olefinic compound and P ^^ methylene bis (tert-butyl) -methylphenyl / phenylphosphite (ligand in Gray No. 3 in Table 6 above) as the catalyst activator ligand. The procedure is as follows for the initiation of the process and the way it is carried out according to the example X above, except that instead of two reactors connected in series, only a single reactor is used, and the feed material is isobutylene as the olefin compound and as the ligand above said phosphite. 1127 ml of catalytic composition consisting of 200 ppm of rhodium in the form of dicarbonylene acetylacetonate, 0.9 wt.% Of [2,2, -methylene-bis- (6-1H-butyl-4-methylphenyl)] phenyl phosphite are introduced into the reactor (about 10 molar equivalents of phosphite ligand / molar equivalent of rhodium), dissolved in a mixture of about 475 ml of pentanal and about 466 g of Texanol®. The data presented in Table 13 below refer to the process conditions and its efficiency expressed in moles of 3- methylbutanal / liter / hour for three days of continuous hydroformylation. 1 Olefin feed, mole% Isobutylene Isobutane Reaction conditions Temperature ° C Tiibela 13 1 2 99.96 0.04 84.8 Process days 2 3 99.94 0.06 84.8 3 4 100 84.834 150 429 1 2 3 4 CisnSnic- 103Pa 1380.87 1401.48 1415.22 HaKfPa 507.83 519.72 451.77 ~ CO103Pa 22.95 54.82 286.07 IsobutyleneK ^ Pa 728.22 674.91 588.00 Results 3-Mctylobutanal, reaction speed mol / liter / hour 1.55 1.60 0.64 Example XIV. Butene-2 is hydroformylated in the same manner as in Example XII above, using as ligand 1, r-binaphthylene-2,2'-diyl- (2,6-di-tert.butyl-4-methylphenyl) phosphoylite (ligand No. 9 in Table 3). The hydroformylation is carried out in a glass reactor in a continuous manner with a single pass. The process concerns the hydroformylation of 2-butene. The reactor consists of a 88.71 ml pressure cylinder immersed in an oil bath with a glass front wall for viewing. After purging the system with nitrogen, about 20 ml of a freshly prepared rhodium catalytic precursor solution is introduced into the reactor using a syringe. The precursor solution contains about 20 ppm of rhodium introduced as dicarbonylene acetylacetonate, about 9.6 molar equivalents of the ligand 1,1-binaphthylene-2-Kliyl- (2,6-cli-tertiary butyl-4-methylphenyl / phosphite / mol) rhodium metal and Texanol & as a solvent. After the reactor has been closed, the system is purged with nitrogen again and the oil heated to the temperature set for the hydroformylation reaction. The hydroformylation reactions are carried out at a total vacuum of about 1099.20 · 103 Pa, the partial pressures of hydrogen, carbon monoxide and 2-butene being given in Table 14 below (the remainder being the pressure of nitrogen and the aldehyde produced). The flow of feed gases (carbon monoxide, hydrogen and 2-butene) is controlled separately for each of them by means of flowmeters, while the gases entering the reactor are dispersed in the precursor solution by means of a sintered glass beam. The unreacted part of the feed gases carries them away. generated aldehydes with 5 carbon atoms in the molecule. The exhaust gas is analyzed over a period of approximately 14 days of continuous operation at the reaction temperature given in Table 14 below. This table also shows the average rate of reaction for each experiment expressed as moles of aldehydes with 5 carbon atoms per liter / hour as Also the molar ratio of n-pentanal produced to the 2-methylbutanal produced Table 14 Test results - daily average Partial pressure Molar ratio Days Tempe-Rod Ligand Rate of lanc.pr./process aldehyde rature ppm%%% 103Pa reaction mole / chain aldehyde ° C x wt * ^^^^ _ ^ __ ^ _ ^^^^^^^ liter / hour branched 102 100 100 100 100 100 100 100 100 100 110 110 110 146 162 163 153 156 186 223 86 171 189 183 215 260 0.7 0.8 0.8 0.8 0.8 0.9 1.1 0.4 0.9 1.9 1.9 1.1 1.3 CO 288.54 219.84 233.58 233.58 219 , 84 226.71 226.71 206.10 233.58 233.58 240.45 240.45 247.32 H2 329.76 267.93 281.67 336.63 267.93 274.80 274.80 254, 19 274.80 267.93 281.67 281.67 288.54 Butene-2 123.66 151.14 16 4.88 171.75 158.01 164.88 171.75 151.14 240.45 247.32 240.45 254.19 261.06 1.10 1.52 1.74 1.79 1.74 1, 68 1.73 1.06 1.80 1.85 1.86 2.08 1.76 0.20 1.30 1.20 1.07 1.18 1.36 1.39 0.84 1.09 1 , 19 1.00 1.12 1.28 0.8 1.6 2.2 3.8 4.5 4.6 6.7 7.7 7.1 10.7 11.8 12.8 13.6 The following notation is used in Table 14 above: 1 The changing values reflect changes in the daily solution levels in the reactor. 1 »4» 35 Example XV. Isobutylene is hydroformylated in the same way as described in Example XII above, using the ligand 1, 1 2,2'-diyl- (2,6-di-tertiarybutyl-4-methylphenyl) phosphite (ligand from example 1). The hydroformylation is carried out in a glass reactor in a continuous, single pass manner. The process concerns the hydroformylation of isobutylene. The reactor consists of a 88.71 ml pressure bottle immersed in an oil bath in front of a glass wall allowing for gliding. After purging the system with nitrogen, about 20 m of a freshly prepared solution of rhodium catalytic precursor is introduced into the reactor by means of a syringe. The precursor solution contains about 250 ppm of rhodium introduced as dicarbonylene acetylacetonate, about 10 molar equivalents of the ligand 1,1-biphenyl-2,2) -diyl- (2,6-di-III-butyl-4-methylphenyl / phosphite / mol) rhodium metal and Texanol® as a solvent. After closing the reactor, the system is purged with nitrogen again and the oil is heated to the temperature set for the hydroformylation reaction. The hydroformylation reactions are carried out at a total pressure of about 1099.20-103 Pa, the partial pressures of hydrogen, carbon monoxide and isobutylene being given in Table 15 below (the remainder being the pressure of nitrogen and the aldehyde produced). The flow of the feed gases (carbon monoxide, hydrogen and isobutylene) is controlled separately for each of them by means of flow meters, the gases entering the reactor being dispersed in the precursor solution by means of a sintered glass beam. The unreacted part of the feed gases carries the formed 3-methylbutanal with it. The exhaust gas is analyzed over a 7-day continuous process conducted at the reaction temperature given in Table 15 below. This table also shows the average rate of reaction for each experiment, expressed in moles of 3-methylbutanal / liter / hour. Table 15 Test Results - Daily Average Process days 0.8 1.7 2.7 3.1 5.8 6.6 7.1 Temperature ° C 99 115 115 115 115 115 115 115 Rod ppmx 179 252 226 207 279 205 210 Ligand% molx 0.8 1, 1 1.0 0.9 1.2 0.9 0.9 CO2 partial pressure 219.84 212.97 178.62 570.21 480.90 494.64 432.81 H2 474.03 583.95 178.62 508.38 501.51 487.77 425.94 • 103Pa Isobutylene 185.49 350.37 659.52 75.57 178.62 178.62 "295.41 Reaction rate mol / liter / hour 1.09 1.46 1.54 1.48 0.68 0.58 0.84 The following notations are used in Table 15: x Changing values reflect changes in the daily levels of the solution in the reactor. Example XVI. [S ^^ Di-III-butyl-S ^^ dimethoxy-1,1'-biphenyl-2,2'-diyl] methyl phosphite of formula 15 is prepared as follows. Solution approximately 90 g (about 0.5 mol) of 2-tert-butyl-4-methoxyphenol and 170 ml of H 2 O containing about 56 g (about 1.0 mol) of potassium hydroxide are heated with stirring to about 80 ° C. Air is then passed through this solution until the diphenol compound, i.e. 2 ^ '- dihydroxy-3-3'-di-III-tert-butyl-5-5'-dimethoxy-l, r- is completely lost. biphenyl. The total reaction time is approximately 135 minutes. Thereafter, the resulting white solid of the biphenol compound is filtered hot and washed twice with about 200 ml of water. About 78 g (87.6% of theory) of the isolated compound, 2,2'-dihydroxy-3,3'-di-tertiary-butyl-5,5''dimethoxy-l, r-biphenyl, are recovered at Melting point around 222-224 ° C. The structure of the compound obtained was confirmed by the IR and MS methods. About 75.2 g of the diol thus prepared in the form of 2,2'-dihydroxy-3,3'-di-tert-butyl-5,5'-dimethoxy-1,3 -biphenyl is then added to about 1 liter of toluene, after which toluene is distilled off in an amount sufficient to azeotropically remove any remaining traces of moisture from the solution. The toluene diol solution is then cooled to 0 ° C, then 70 g of triethylamine are added, and then, at 0 ° C for about 20 minutes, about 29 g of phosphorus trichloride are added dropwise. The reaction mixture obtained thickens with triethylamine hydrochloride. It is heated for about 30 minutes at a temperature of about 100 ° C. The suspension is then cooled to a temperature of about 55 ° C and about 13.44 g of methanol are added to it over a period of about 15 minutes. The whole is heated for about one hour at a temperature of about 90-95 ° C, then filtered hot to remove the triethylamine hydrochloride sediment. The filtrate obtained is evaporated to dryness under reduced pressure, and the resulting residue is dissolved in about 100 ml. acetonitrile under a reflux condenser and cooled to remove the desired ligand [SjS ^ i-in-raed.butyl-SjS ^ methoxy-ljl ^ biferiyl-i ^^ jil] - methyl phosphite, from which about 75 g of the desired compound are recovered (85 , 4% of theory). It was found that the set, crystalline phosphite ligand shows a melting point of about 64-69 ° C and a characteristic phosphite resonance in 3 PNMR, corresponding to 131.9 ppm (relative to external H3PO4). Example XVII. The following diorganophosphite ligands are prepared in the same manner as described in Example XVI above, except, of course, that hydroxyl reactants corresponding to and responsible for the structure of diorganophosphites are used. Ligand A (formula 20) [3,3'-di -III-cced.butyl-5.5'Ktimethoxy phenyl. A crystalline compound, m.p. 131-132 ° C. It shows a characteristic phosphite resonance in 31 PNMR, corresponding to 140.1 ppm (relative to external H3PO4). Ligand B (formula 22) [3,3'-di-III-order butyl-5,5'-dimethoxy-M Non-crystalline compound with gum consistency, showing the characteristic phosphite resonances at 31 PNMR, corresponding to 140.1 ppm and 139.9 ppm (relative to external H3PO4). In this case, the term "nonyl" denotes a branched-chain mixture of nonyl radicals. Ligand C (Formula 25) [3,3'-di-tertiary-butyl-5,5'-dimethoxy-1,3-biphenyl- 2,2'-Diyl] phosphite / J-naphthyl A non-crystalline compound with a rubbery consistency, showing a characteristic phosphite resonance in 31PNMR, corresponding to 139.2 ppm (relative to external H3PO4). Example XVIII. Butene-2 is hydroformylated in this manner. the same method as described in the above example XII, using as ligand [3,3'-di-tertiarybutyl-5,5'-dimethoxy-11lT ^ phenyl ^^ - methyl diylphosphite (ligand from example XVI). Hydroformylation is carried out by The process involves the hydroformylation of 2-butene The reactor consists of a 88.71 ml pressure cylinder immersed in an oil bath with a glass front wall allowing for peeking. The reactor, after purging the system with nitrogen, is introduced with the use of nitrogen. syringes about 20 ml of freshly prepared rhodium solution of the catalytic precursor. The precursor solution contains about 250 ppm of rhodium introduced as dicarbonylene acetylacetonate, about 2.0 wt% ligand (about 19.7 molar equivalents [3,3'-di-III-tier-butyl-5,5'-dimethoxy-1, Methyl Hiphenyl-2,2'-diyl] phosphite (mole of rhodium metal) and trimeric pentanal as solvent After closing the reactor, the system is purged with nitrogen again and the oil bath is heated to the temperature set for the hydroformylation reaction. a total pressure of approximately 1099.20 · 10 Pa, with the partial pressures of hydrogen, carbon monoxide and 2-butene given in Table 16 below (the remainder is the pressure of nitrogen and the produced aldehyde). The flow of the feed gases (carbon monoxide, hydrogen and butene-) 2) are controlled separately for each of them by means of flowmeters, with the gases entering the reactor being dispersed in the precursor solution by means of a sintered glass beam. [Unreacted part from the supply gases, it carries away the formed aldehydes containing 5 carbon atoms in the molecule. The exhaust gas is analyzed over a period of about 11 days of a continuous process at a reaction temperature of about 90 ° C, shown in Table 16 below. This table also shows the average rate of reaction for this experiment expressed in moles of aldehydes produced with 5 carbon atoms in the molecule / liter / hour, as well as the molar ratio of the produced straight-chain n-pentanal to branched-chain 2-methylbuttanal 150 429 Table 16 Test results - daily average Partial pressure days Process temperature ° C 103Pa CO Ha Butene-2 Reaction rate mol / liter / hour Mole ratio straight-chain aldehyde / clear-lance aldehyde 0.5 3.5 4.5 5.5 6.5 7.5 10.5 10.9 90 90 90 90 90 90 90 90 178 , 62 137.40 137.40 137.40 137.40 144.27 137.40 137.40 494.64 405.33 4123 4123 4123 4123 4123 398.46 68.70 82.55 68.70 68.70 68 , 70 82.44 68.70 82.44 0.7 1.7 W 1.5 1.7 W 1.6 1.9 0.3 0.7 0.6 0.6 0.6 0.7 0 , 6 0.7 Example XIX. Butene-2 is hydroformylated in the same manner as in Example XII above, using the ligand [3,3H-tertiarybutyl-5,5'-dimethoxy-1,4-biphenyl-2,2 ' -diyl] phenyl phosphite (ligand A of example XVII). The hydroformylation is carried out in a glass reactor in a continuous process with a single pass. The process concerns the hydroformylation of 2-butene. The reactor consists of an 88.71 ml pressure cylinder immersed in an oil bath with a glass front wall for viewing. After purging the system with nitrogen, about 20 ml of a freshly prepared rhodium catalytic precursor solution is introduced into the reactor using a syringe. The precursor solution contains about 250 ppm of rhodium introduced in the form of dicarbonylene acetoacetate, about 2.0 wt.% Of the ligand (about 17.2 molar equivalents of the ligand [S ^^ di-III-tert-butyl-SjS'-dimethoxy-l, r- biphenyl-2,2'-diyl] phosphin-phenyl (mole of rhodium metal) and trimeric pentanal as solvent After the reactor is closed, the system is purged with nitrogen again and the oil bath is heated to the temperature set for the hydroformylation reaction. about 1099.20 • 103 Pa, with the partial pressures of hydrogen, carbon monoxide and 2-butene given in the following table 17 (the remainder is the pressure of nitrogen and the produced aldehyde). The flow of the feed gases (carbon monoxide, hydrogen and 2-butene) controls for each of them by means of flowmeters, where the gases introduced into the reactor are dispersed in the precursor solution by means of a sintered glass beam. c of the feeding gases carries away the formed aldehydes containing 5 carbon atoms in the molecule. The exhaust gas is analyzed over a period of approximately 13 days of continuous operation at a reaction temperature of approximately 90 ° C as shown in Table 17 below. This table also shows the average reaction rate for this experiment expressed as moles of aldehydes produced with 5 carbon atoms per molecule. ce / liter / h, as well as the molar ratio of the straight-chain n-pentanal produced to the branched-chain 2-methylbutanal. The analysis performed after 2.5 days of the process showed a poor inflow of butene-2 as a result of clogging of the gibs. The case was cleared and the reactions continued. Table 17 Test results - daily averages Process days 1 Temperature ° C 2 Partial pressure • 103Pa CO H2 Butene-2 3 4 5 Reaction rate mol / liter / hour 6 Straight chain aldehyde / aldehyde molar ratio with branched lance 7 0.5 1.5 2.5 90 90 90 158.01 137.40 95.41 446.55 412.20 41.22 68.70 61.83 6.87 1.4 1.8 0.04 0.7 0.8 -38 150 429 1 5.5 6.5 7.5 8.5 9.5 12.5 12.9 2 90 90 90 90 90 90 90 3 144.27 144.27 144.27 151.14 151.14 144.27 144.27 4 405.33 405.33 412 ^ 0 412.20 412.20 412.20 4123 5 96.18 89.31 82.44 82.44 68, 70 82.44 89.31 6 1.8 2.0 1.8 1.9 1.8 1.8 1.7 7 0.8 0.8 0.7 0.7 0.7 0.7 0, 7 Example XX. Butene-2 is hydroformylated in the same manner as in Example XII above, using as the ligand [3,3'-di-III-butyl-5,5'-dimethoxy-l, r-biphenyl-2,2 ' -diyl] 4-nonyl phosphite (ligand B of example XVII). The hydroformylation is carried out in a glass reactor in a continuous manner with a single pass. The process concerns the hydroformylation of 2-butene. The reactor consists of a 88.71 ml pressure cylinder immersed in an oil bath with a glass front wall for viewing. After purging the system with nitrogen, about 20 ml of freshly prepared rhodium catalytic precursor is introduced by means of a syringe into the reactor. The precursor solution contains about 250 ppm of rhodium introduced in the form of dicarbonylene acetylacetonate, about 2.0 wt% of the ligand (about 13.6 molar equivalents of the ligand [3,3'-di-1H-butyl-5,5'-dimethoxy-1, r-biphenyl-2,2'-diyl] 4-nonyl phosphite / mole of rhodium metal) and trimmetric pentanal as solvent. After the reactor is closed, the system is purged with nitrogen again and the oil bath is heated to the temperature set for the hydroformylation reaction. The hydroformylation reactions are carried out at a total pressure of about 1099.20 bar, the partial pressures of hydrogen, carbon monoxide and 2-butene as given in Table 18 (the remainder being the pressure of nitrogen and the aldehyde produced). The flow of the feed gases (carbon monoxide, hydrogen and 2-butene) is controlled separately for each of them by means of flowmeters, the gases entering the reactor being dispersed in the precursor solution by means of a sintered glass beam. The unreacted part of the feed gases carries away the formed aldehydes containing 5 carbon atoms in the molecule. The exhaust gas is analyzed over a period of approximately 13 days of continuous operation at a reaction temperature of approximately 90 ° C as shown in Table 18 below. This table also shows the average rate of reaction for this experiment expressed in moles of aldehydes produced with 5 carbon atoms per molecule / liter / hour as well as the molar ratio of n-pentanal with a straight chain to 2-methylbutanal with a branched chain. Table 18 Test results - daily average Partial pressure Days Process temperature ° C • 10 * Pa CO H2 Butene-2 Reaction rate mol / liter / h Mole ratio straight-chain aldehyde / expanded lance aldehyde 0.5 1.5 2.5 5.5 6.5 7.5 8.5 9.5 12.5 12.9 90 90 90 90 90 90 90 90 90 90 137.40 109.92 103.05 109.92 109.92 116.79 109.92 116.79 109.92 109.92 412.20 480.90 480.90 467.16 474.03 480.90 480.90 480.90 480.90 480.90 103.05 82.44 103.05 103.05 96.18 82.44 89.31 82.44 96.18 89.31 1.0 U 1 , 5 1.7 1.8 1.7 - 1.8 1.6 1.7 1.5 0.7 1.0 1.0 1.5 1.5 1.5 1.5 1.5 1, 6 1.7 Example XXL E A continuous hydroformylation experiment, similar to the experiment in Example X above, is carried out using isobutylene as the olefin compound and [3,3 H -di-III-tert-butyl-5,5 H -dimethoxy-l, r -biphenyl-2,2H-diyl] phosphite (ligand from example XVI as above) as a catalyst activator ligand. The above example X is followed, both for the initiation of the process and the method of carrying it out. The hydroformylation reactions are carried out as follows. About 1.03 liters of a catalytic precursor solution containing dicarbonyl rhodium acetylacetonate (about 450 ppm of rhodium), about 2.8 wt.% Of the ligand in the form of [S ^^ - di-III-proprietary-S ^ '- dimethoxy-1,3-biphenyl-2,2H-diyl] methyl phosphite (about 15.3 mole equivalents of ligand / mole of rhodium), about 2.0% by weight of triphenylphosphine oxide as internal standard and about 95.8% by weight of aldehyde containing 5 carbon atoms in the molecule (about 82.8 wt% pentanal and about 13.0 wt% trimeric pentanal) as solvent. Approximately 1.2 liters of the same catalytic precursor solution are charged to reactor 2. The reactor system is then purged with nitrogen to remove any oxygen present in the system. Nitrogen is then introduced into both reactors under a pressure of about 687.00 · 103 Pa and the reactors are heated to the predetermined reaction temperature given in Table 19 below. Purified hydrogen, carbon monoxide and isobutylene ( the composition of isobutylene, which is the raw material in the described process, contains at least 99.9 mol% or more of isobutylene, and the rest is isobutane) and the pressure in the reactor increases to the value of the working pressure given in Table 19. When the liquid level in reactor 1 begins to rise in as a result of the formation of liquid aldehyde product of the reaction, part of the reaction solution is then pumped from reactor 1 to reactor 2 through the conduit leading to the top of reactor 2, at a rate sufficient to maintain a constant liquid level in reactor 1. The pressure in reactor 2 is increased to the pressure value in table 19. The quantity is measured and the composition of the exhaust gas is tested from reactor 2. At a controlled flow rate, ready-to-use synthesis gas (CO and H2) is introduced in order to maintain the desired partial pressure of both components in reactor 2. During the hydroformylation reaction, the operating pressure and temperature are kept constant. reaction. When the liquid level in reactor 2 begins to rise due to the formation of liquid aldehyde product of the reaction, part of the reaction solution is pumped to the vaporizer / separator at a rate sufficient to maintain a constant liquid level in reactor 2. The resulting crude aldehyde separates from of the reaction solution at various temperatures, condensed, and collected in the product receiver. The remaining non-evaporated catalyst-containing reaction solution is recycled back to reactor 1. The hydroformylation experiment is carried out continuously for 33 days. During the first 15 days of the process, the aldehyde formed is separated from the reaction solution at a temperature of about 115 ° C. and a pressure of 151.14-178.62-103 bar, then, from day 16 to 19, isolation is carried out at about 117 ° C. C and under a pressure of 151.14-178.62-103 Pa, from 19 to 22 days the precipitation is carried out at a temperature of about 123 ° C and a pressure of 151.14-178.62 • 103 Pa and from 23 to 32.5 days the precipitation is carried out at a temperature of 133 ° C and a pressure of 151.14-178.62-103 Pa. The data presented in Table 19 give the conditions in which the process is carried out and its efficiency expressed in moles of 3-methylbutanal produced / liter / hour during approximately 33 days of hydroformylation Table 19 Process days 1 Reactor No. 1 Temperature ° C Pressure-103 Pa Ha-HfPa CO-103Pa Isobutylene -103 Pa Rsaktpr No. 2 Temperature ° C 6.9 2 95.0 1270.95 499.45 397, 77 235.64 95.3 13.9 3 - - 95.0 1270.95 486.39 379.22 257.62 95.4 21.8 4 .. ... 94.9 1270.95 485.02 364.79 272.74 95.5 32.5 5 95.5 1270.95 429 , 37 384.03 322.20 95.440 150 429 1 Pressure -103 Pa H2-103Pa COltfPa Isobutylene-103Pa Results 3-Methylbutanal / mol / liter / hour 2 1133 ^ 55 524.18 332.51 94.12 1.77 3 1133.55 515.25 297.47 105.80 1.81 4 1133.55 501.51 338.00 112.67 U4 5 1133 ^ 55 454.11 368.23 166.94 1.49 Resource of rhodium in the reactor system is monitored daily throughout the experiment and during the first 26 days of continuous hydroformylation no detectable loss of rhodium in the system is observed. However, prolonged studies show that the reactor system has a loss of about 10% of the rhodium resource in the course of the reaction continuously from 26 to 32.5 days (end of the experiment). The above experiment shows that the activity and stability of the rhodium complex catalyst obtained by using as the ligand of [3,3'-di-rtc. butyl-5'H-dimethoxy-1,3'-biphenyl-2,2'-diyl] methyl phosphite, it is high even when it comes to hydroformylation of a normally highly unreactive olefin compound such as isobutylene. Moreover, this experiment shows that the use of a compound such as [3,3'-di-tert.butyl-5,5'-dimethoxy-1,3'-biphenyl-2'-diyl] phosphite methyl as a ligand allows the isolation of crude aldehyde produced from the reaction solution at an evaporation temperature even as high as above 120 ° C without any loss of the rhodium resource over an extended duration of the process, with the uniform production of 3-methylbutanal showing a high stability of the ligand in terms of decomposition. situ phosphite to an undesirable by-product in the form of hydroxyalkylphosphonic acid. Example XXII. Butene-1 is hydroformylated in the same manner as in Example XII above, using [3,3'-di-tert.butyl-5.5, -dimethoxy- U'-biphenyl-2,2'-diyl as the ligand ] O-naphthylphosphoyl (ligand C of example XVII). The hydroformylation is carried out in a glass reactor by a continuous method with a single pass. The process concerns the hydroformylation of butene-1. The reactor consists of an 88.71 ml pressure cylinder immersed in an oil bath with a glass front wall for viewing. To the reactor, after purging the system with nitrogen, about 20 ml of a freshly prepared solution of rhodium catalytic precursor are introduced using a syringe. The precursor solution contains about 25 ppm of rhodium introduced as dicarbonylene acetylacetonate, about 2.0 wt% of the ligand (about 155 molar equivalents [S ^^ di-III-butyl-S ^^ methoxy-l,! '-Biphenyl-2, 2'-diyl] phosphite / J-naphthyl / mol of rhodium metal) and trimeric pentanal as solvent. After closing the reactor, the system is purged with nitrogen again and the oil bath is heated to the desired hydroformylation reaction temperature. The hydroformylation reactions are carried out at a total pressure of about 1099.20-103 Pa, the partial pressures of hydrogen, carbon monoxide and 1-butene being given in Table 20 below (the remainder being the pressure of nitrogen and the aldehyde produced). The flow of feed gases (carbon monoxide, hydrogen and 2-butene) is controlled separately for each of them by means of flowmeters, while the gases entering the reactor are dispersed in the precursor solution by means of a sintered glass beam. The unreacted part of the feed gases carries away the formed aldehydes containing 5 carbon atoms in the molecule. The exhaust gas is analyzed over a period of approximately 14 days of a continuous process carried out at a reaction temperature of approximately 90 ° C, shown in Table 20 below. This table also shows the average rate of reaction for each experiment, expressed as moles of aldehydes produced with 5 carbon atoms in the molecule / liter / hour, as well as the molar ratio of the straight chain n-pentanal produced to the branched chain 2-methylbutanal produced. It is believed that the reduction in the reaction rate for the production of aldehydes with 5 carbon atoms in the molecule with time should be related to the very low rhodium concentration used in this experiment 150 429 41 Table 20 Test results - daily mean Partial pressure Molar ratio Days Temperature * 103Pa Reaction rate of the process chain aldehyde. ° C ¦. ¦ mol / liter / h straight line / aldehyde CO H2 Butene-1 with spigot lance 4.0 4.0 3.7 4.0 4.0 5.0 6.0 7.0 8.0 W 9.0 8 . 0 8.0 8.0. Example XXIII. The hydroformylation experiment is carried out in a continuous manner, similar to the experiment in Example X above, and the formation of hydroxyalkylphosphonic acid is monitored. Hydroformylation reactions are carried out as follows. About 770 ml of a precursor catalytic solution containing dicarbonyl rhodium acetylacetonate (about 492 ppm of rhodium), about 3.5% by weight of ligand in the form of 1,1-biphenyl-2,2'-diyl- / 2,6-di is introduced into reactor 1. -III- butyl-4-methylphenyl / phosphite order (about 16.8 molar equivalents of ligand / mol of rhodium) and about 96.3% by weight of an aldehyde containing 5 carbon atoms in the molecule (about 69.3% by weight of pentanal and about 27% by weight) in trimeric pentanal) as solvent. About 900 ml of the same catalytic precursor solution are introduced into reactor 2. In addition to starting the process and the method of carrying it out, the above example X is followed. The conditions of the hydroformylation reaction, as well as the rate of formation of aldehydes containing 5 carbon atoms in the molecule expressed in moles / liter / hour, as well as the molar ratio of straight-chain aldehyde ( n-pentanal) to the branched-chain aldehyde (2-methylbutanal) are given in the following table 21 Table 21 Process days 1 Butane feed,% mol Butene-1 Trans-butene-2 Cis-butene-2 Reactor No. 1 Temperature ° C Pressure-103 Pa H2-103Pa CO-103Pa Butene-1 Trans-butene-2 and cis-butene-2 • 103Pa Reactor No. 2 Temperature ° C Pressure-103 Pa H2-103Pa CO103Pa 7 2 41.9 35.1 22, 9 70.4 1 408.35 609.37 135.34 26.79 267.24 90.7 1270.95 612.12 59.08 U 3 37.4 38.2 24.4 65.6 1 408.35 593, 37 226.71 38.47 272.74 95.5 1270.95 535.17 159.38 12 4 40.2 36.4 23.4 65.1 1408.35 566.09 322.20 66.64 270, 69 95.3 1270.95 478.84 272.74 0.5 1.5 2.5 3.5 4.5 5.5 7.5 8.5 9.5 10.5 11.5 12.5 13 , 5 13.9 90 90 90 90 90 90 90 90 90 90 90 90 90 90 82.44 61.83 54.96 61.83 68.70 75.57 82.44 82.44 82.44 82.44 82.44 82.44 82.44 82.44 302, 28 274.80 261.06 281.67 288.54 288.54 295.41 295.41 302.28 295.41 295.41 302.28 302.28 295.41 261.06 249.45 206.10 171 , 75 192.36 199.23 206.10 137.40 185.49 192.36 192.36 192.36 192.36 199.23 W 1.5 1.7 1.5 U 1.0 0.7 0 , 5 0.5 0.5 0.6 0.5 0.5 0.442 150 429 1 Butene-1-103 Pa Trans-butene-2 and cis butene-2-103 Pa Results The rate of production of aldehydes containing 5 carbon atoms in the molecule , mol / liter / hour Mole ratio of straight chain aldehyde / branched chain aldehyde 2 9.62 254.88 2.89 1.87 3 15.80 316.70 / 2.76 1.34 4 15 , 11 341.44 2.31 1.39 In this hydroformylation experiment, the hydroformylation reaction environment is monitored by periodically sampling the catalyst containing hydroformylation reaction environment in reactor 1 and testing them using the 31PNMR method. on the detectable signal (resonance peak) of α-hydroxy acid pentylphosphonic acid. A standard synthetic solution containing 100 ppm (w / v) of α-hydroxypentylphosphonic acid is used as a standard, which gives a detectable signal of phosphonic acid (resonance peak) corresponding to approximately 25.8 ppm relative to external H3PO4 at 31PNMR after 2000 pulses (pass). This means a low detection limit of α-hydroxypentylphosphonic acid at a concentration of approximately 100 ppm (w / v). After approximately 10 days of continuous hydroformylation, no detectable amount of α-hydroxypentylphosphonic acid is detected by the 31PNMR method. However, on the eleventh day of this continuous process, a small amount of α-hydroxypentylphosphonic acid is formed as evidenced by the appearance of a small resonance peak of phosphonic acid in the 31P NMR spectrum examined that day. On the eleventh day, the Amberlyst • A-21 resin exchange is used in the form of a bed placed on the route of the catalyst return line in the process with liquid recycle and the catalyst-containing recycle solution, after removal of the desired aldehyde constituting the reaction product, during the return passes into the reactor through said bed. Within a few hours, the hydroformylation reaction medium is cleared of α-hydroxypentylphosphonic acid, as evidenced by the disappearance of the detectable peak of phosphonic acid in the 31P NMR spectrum (in a sample taken from the hydroformylation environment) recorded on day 12. It should be noted that technically pure Amberlyst® A-21 resins are used in this experiment. Of course, this resin contains chloride impurities which contaminate (poison) part of the rhodium catalyst, as evidenced by the presence of new peaks of the rhodium-ligand complex in the 31P NMR spectrum study. Example XXIV. The hydroformylation experiment is carried out in a continuous manner, similar to the experiment shown in Example X above, and the formation of hydroxyalkylphosphonic acid is monitored. The hydroformylation reactions are carried out as follows: About 770 ml of precursoratalytic solution containing dicarbonyl peridicarbonyl acetylacetonate is introduced into reactor 1. ppm of rhodium), about 2.0 wt.% ligand in the form of 1,1'-biphenyl-2,2'-diyl- (2,6-di-tert-butyl-4-methylphenyl) phosphite (about 15.8 molar equivalent ligand / mole of rhodium) and about 98 wt% of an aldehyde having 5 carbon atoms in the molecule (about 70 wt% pentanal and about 28 wt% trimeric pentanal) as solvent. About 900 ml of the same catalytic precursor solution are introduced into the reactor 2. As for the initiation of the process and the method of carrying it out, the above Example X is followed. In this experiment, a purified ion exchange resin in the form of Amberlyst® A-21 is used from the start of the process. The resin bed is placed on the catalyst recycle line, so that the recycle of the reaction medium containing the catalyst, after removing the desired aldehyde constituting the reaction product, passes through the said bed during its return to the reactor. On the first day of the process, an additional amount of the same phosphite ligand is added to compensate for the low concentration of it in the starting feed. 150 429 43 On the seventh day of the process, the Amberlyst resins are replaced with a new bed of purified Amberlyst® A-21 ion exchange resin. On the eighth day, the system ceased to operate on two hours due to a power cut. On the fourteenth day, the rhodium complex catalyst was removed from both reactors because the indications for liquid level control seemed erroneous. On the fifteenth day, fresh dicarbonylodine acetylacetonate is added to increase the rate of reaction, and an additional amount of the same phosphite ligand as used in this experiment is added to maintain the intended concentration. Hydroformylation reaction conditions as well as the rate of formation of carbon aldehydes containing 5 carbon atoms in the molecule expressed in moles / liter / hour, as well as the molar ratio of the straight-chain aldehyde (n-pentanal) produced to the branched-chain aldehyde (2-methylbutanal) produced are given in Table 22 below. Table 22 Feed butene,% mol Butene-1 Trans-butene-2 Cis-butene-2 Reactor no.1 Temperature ° C Pressure-103 Pa H2-103Pa CO103Pa Butene-1-103Pa Trans-butene-2 and cis-butene-2 • 103Pa Reactor no.2 Temperature ° C Pressure • 103 Pa H2-103Pa CO-103Pa Butene-1, -103Pa Trans-butene-2 and cis-butene-2-103 Pa Results Production rate of aldehydes containing 5 carbon atoms in the molecule, mol / liter / hour Molar ratio aldeh straight chain yd / branched chain aldehyde 7 42.6 34.6 22.8 85 1408.35 593.57 188.93 46.72 361.36 95.2 1270.95 537.23 103.74 18.55 364.11 3.31 1.59 Process days 16 46.1 30.5 23.3 85.5 1408.35 639.59 55.65 43.97 390.22 95.3 1270.95 485.71 103, 05 24.73 457.54 3.15 1.91 22 43.5 32.5 24.0 85.4 1408.35 598.38 87.25 50.15 420.44 96.7 1270.95 474.03 109.92 26.11 481.59 3.01 1.81 In this experiment, the hydroformylation reaction environment is monitored for the presence of α-hydroxypentylphosphonic acid by the 31PNMR method as shown in Example XXIII. The 31PNMR spectra of the reaction environment samples taken from reactor 1 on days 7, 16 and 22 of the continuous process showed no detectable amounts of the breakdown product of α-hydroxypentylphosphonic acid. Moreover, in this experiment, a bed of technically pure Amberlyst® A-21 resin was cleaned with a series of washes prior to use to remove chloride and aluminum oxypolymer (oligomers) impurities. The resins are purified as follows. Glass column 50 cm X 36 mm, fitted with a stopcock, 250 g (630 ml) of resin are loaded with a glass wool plug and washed with the following solvents at the indicated rate of bed volume / hour: a) 3 bed volumes (1890 ml ) 10% hydrochloric acid, b) 4 bed volumes (2520 ml) 5% sodium hydroxide, c) 5 bed volumes (3150 ml) deionized water, d) 4 bed volumes (2520 ml) methanol, e) 3 bed volumes (1890 ml) toluene. The resins are then removed from the column and placed in a 1 liter flask and dried at a temperature of about 40 ° C and a pressure of 13.33-102 Pa using a rotary evaporator. In the experiment in which the purified Amberlyst®A-21 resin was used, no rhodium-chloride complexes were found in the 31PNMR spectrum.44 150 429 Claims 1. Method of hydroformylation of an ethylenically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a transition metal complex catalyst from the VIII group with a phosphate ligand to give aldehydes, characterized in that the hydroformylation of the ethylene compound is carried out in the presence of a catalyst consisting of a complex consisting of rhodium complexed with carbon monoxide and a diorganophosphite ligand of formula I, in which W is an alkyl radical of 1- 18 carbon atoms optionally containing one or more phenyl, cyano, halo, nitro, trifluoromethyl, hydroxyl, amino, -COR6, where R6 is an alkyl group of 1-10 carbon or phenyl, carbonyloxy, oxycarbonyl, sulfonyl, sulfonyl, sulfonyl , sulfinyl, silyl, ether, phosphonyl, thions or W is an alpha-naphthyl radical, a beta-naphthyl radical or a radical of formula 6 in which X1, X2 and Z4 each represent a hydrogen atom, an alkyl, phenyl, benzyl, cyclohexyl, 1-methylcyclohexyl, cyano, halogen radical, nitro, trifluoromethyl, hydroxyl, amine, -COR6, where R6 is as defined above, carbonyloxy, oxycarbonyl, amide, sulfonyl, sulfinyl, silyl, ether, phosphonyl or thionyl radical, and Ar is the same or different. aryl substituted with one or more of the substituents given above for X1, X2 and Z4, Q is a divalent bridging group, such as -CR1R2- or -S-, wherein R1 and R2 are each individually hydrogen or an alkyl radical of 1 12 carbon atoms, n is a number 0 or 1, and in the presence of added free diorganophosphite ligand of formula I, wherein W, Ar, Q and n are as defined above. 2. The method according to claim The process of claim 1, wherein the ethylenically unsaturated compound is a compound such as alpha-olefins with 2-20 carbon atoms, internal olefins with 4-20 carbon atoms, and mixtures of such internal alpha-olefins. 3. The method according to p. The process of claim 1, characterized in that the hydroformylation reactions are carried out at a temperature of about 50-120 ° C, under the total pressure of a gas mixture consisting of hydrogen, carbon oxide and an ethylenically unsaturated organic compound of about 6.87-10 -10305.00 • 10 Pa, the partial pressure of hydrogen about 103.05'103-1099.20 * 103 Pa and the partial pressure of carbon monoxide about 6.87 • 103-824.40 • 103 Pai in the presence of about 4-50 mol of diorganophosphine ligand / mol of rhodium in the environment reaction. 4. The method according to p. The process of claim 1, wherein part of the hydroformylation reaction fluid is removed from the formylation reaction zone, treated with a weakly basic ammonium resin and returned to the reaction zone. 5. The method according to p. The process of claim 4, wherein the hydroformylation reactions are carried out with continuous recycle of the catalyst-containing fluid. 6. The method according to p. The process of claim 4 or 5, characterized in that the aldehyde compound is released from the removed part of the hydroformylation reaction fluid with the aid of a weakly basic anion exchange resin. 7. The method according to p. 6. The process of claim 6, wherein the weakly basic anion exchange resin is a cross-linked H-amine polystyrene anion exchange resin of the gel or macroreticulum type. 8. The method according to p. The ligand of claim 1, wherein the rhodium-complexed diorganophosphite ligand and the free diorganophosphite ligand are separately used ligands of formula II, in which Q is a group of formula -CR1R2, where R1 and R2 are each separately hydrogen or an alkyl radical with 1-12 carbon atoms, n is 0-1, Y1, Y2, Z2 and Z3 each represent hydrogen, an alkyl radical of 1-18 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl, alicyclic and ether groups, with the proviso that the radical Y1 or Y2 has a spatial hindrance in the form of an isopropyl group or more, and W is a substituted or unsubstituted alkyl radical. 9. The method according to p. A process as claimed in claim 8, characterized in that the olefinic starting compound is butene-1, butene-2, isobutylene and an olefin mixture consisting essentially of butene-1 and butene-150 429 45 2, and the compound of formula 2 is used as the phosphorus ligand, where Q is -CH2- or -CHCH3, Y1 and Y2 are branched alkyl radicals with 3-5 carbon atoms and W is an unsubstituted alkyl radical with 1-10 carbon atoms. 10. The method according to p. The process as claimed in claim 9, characterized in that the compound of formula 2 is used, wherein Y1 and Y2 represent IIF-butyl radicals, Q is -CH2- and W is an unsubstituted alkyl radical with 1-8 carbon atoms. 11. The method according to p. 8. The process according to claim 8, characterized in that the compound of formula 2 is used in which Y1 and Y2 represent t-butyl radicals, Q is -CH2- and W is an alkyl radical substituted with a phosphonyl group of formula -CH2PO / R3 / 2, in which each R3 the same or different and individually represents an alkyl or phenyl group, one of the R3 groups may also be hydrogen. 12. The method according to p. The method of claim 11, characterized in that a compound of formula 2 is used, in which W is a radical of formula -CH2P / O / / C6H5 / 2, and the other symbols have the meaning given above. 13. The method according to p. 3. The ligand according to claim 1, characterized in that as the diorganophosphite ligand complexed with rhodium and the free diorganophosphite ligand, ligands of formulas 3 and 4 are used separately, in which Q represents a group of formula -CR1R2, in which R1 and R2 are each separately hydrogen, the radical alkyl of 1-12 carbon atoms, and n is the number O1, X ', X ", Y \ Y", Z', Z 'and Z ° each separately represent hydrogen, alkyl group with 1-18 carbon atoms, phenyl, benzyl , cyclohexyl, 1-methylcyclohexyl, hydroxyl, carbonyloxy and ether groups, provided that simultaneously at least two radicals X1 and X2 or at least two radicals Y1 and Y2 are radicals hindered in the form of an isopropyl group or more, and also with that in formula III, no more than three radicals such as X1, X2, Y1 or Y2 are hindered radicals in the form of an isopropyl group or more. 14. The method according to p. The process as claimed in claim 13, characterized in that the compound of formula 3 or 4 is used in which Q is -CH2- or -CHCH3- and Y1 and Y2 are branched chain alkyl radicals containing 3-5 carbon atoms. 15. The method according to p. The process of claim 13, wherein the olefinic starting material is butene-1, butene-2 and isobutylene, and an olefin mixture consisting essentially of butene-1 and butene-2, and a compound of formula 3 or 4 wherein Q is - CH2-, and X1, X2, Y1, Y2, Z1, Z2 and Z3 are each hydrogen, an alkyl radical of 1-8 carbon atoms, hydroxyl, carbonyloxy and ether groups. 16. The method according to p. A method according to claim 15, characterized in that the diorganophosphite ligand is a compound of formula 12, 12a and 12b, in which Q is the group -CH2- and n is the number 0 or 1. 17. A method of hydroformylating an ethylenically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a catalyst comprising a complex of a transition metal from group VIII with a phosphate ligand to form aldehydes7, characterized in that the hydroformylation of the ethylene compound is carried out in the presence of a catalyst consisting of a complex consisting of rhodium complexed with carbon monoxide and a diorganophosphite ligand in which Q of formula 5 represents -CH2- or -CHCH3-, each R6 is an alkyl radical of 1-10 carbon atoms, Y1 and Y2 each individually hydrogen, a branched chain alkyl radical of 3-12 carbon atoms, phenyl, benzyl, cyclohexyl and l- methylcyclohexyl, W is an aryl radical of formula 6, where X1, X2 and Z4 are each separately hydrogen, an alkyl radical of 1-18 atoms in gla, optionally substituted aryl, alkaryl, aralkyl and alicyclic radicals, cyano, halogen or ether groups, provided that simultaneously at least two X1 and X2, or at least two Y1 and Y2 in a given Uganda are hindered radicals , in the form of an isopropyl group or more, and provided that no more than three X1, X2, Y1 or Y2 are hindered radicals in the form of an isopropyl group or more and in the presence of an added free diorganophosphite ligand of formula 5, wherein W , Q, Y1, Y2, R6 have the meaning given above. 150 429 (Ar) Ov I \ (a) n pow (Ar) ia) n pow Y2 FORMULA 2 ^ 4 FORMULA 1: A Z2 ^ ° \ LY WZdR 3 ^ CH2CH2x —NO → CH2CH2 FORMULA 7 / CH2-CH2 —N \ / CH2CH2x CH2CH2 / * C —CHo II * ODR 8 WZdR 9 OI! - N ^ C — CH2 XC — CH2 WZdR 10 WZdR 4 WZdR 11 (Qn t-C4Hg ^ P- ° -0-CH3 ¦V Uc4H9 WZdR 12 FORMULA 5 150 429 t - C4H9? -C4H9-O ° v t- <* Hg-0 ° t-C4Hg WZ0R 12a CH3O CH3O t-Bu; po-ch3 t-Bu FORMULA 15 t-Bu CH3 ° - ^ 0 ° ^ rf ^ f% t_rH J \ ^ / MM— ° \ 139 l ^ n P-O ^ Q-CH3 CH3CHO <OO ° ^ I- Bu P-0- (CH2) 17CH3 WZ0R 12b l— Bu HO HO ^ D o • ^ - © t- Bu WZCfR 13 FORMULA 16 t-Bu CH ^ O— (C) 0.CH2 P -O-CH3 / —er WZdR 17 t-: K30 - H3 CH; CH3 ° -0 "t-Bu H0-O 0, HO-O, P-0-CH3 I t-Bu FORMULA U t-Bu FORMULA 18150 429] -Bu t-amyl \ / P- °" HQ ^ ° CH3 ^ J / -O-CH3 CH3 ° -0 ° CH3 ° -0 "t-Bu WZtfR 19" "-O CH30 t-Bu WZtfR 20 t- Bu CH3O-O ° v CHoO - ° ^ O ^ 0CH3 P- 0 ~ CH3 I P-0 CH3 ° ^ 0 ° t-Bu t-Bu FORMULA 21 WZtfR 25 t-Bu ch3 ° -— ° ^ CH30-O o '- ° ^ 0 ^ C9Hl9 CH3O CH3O t - Bu 1 p- ° ^ O ^ ocH3 t — Bu CHo— Ph FORMULA 22 FORMULA 26150 429 Ph ch3ohQ o. T-Bu t-Bu \ t-Bu- P-0- Ph WZdR 27 l-Bu t- Bu y 0 t-Bu WZ (5R 33 0. t-Bu CH3 \ F y f- ° -0 ^ CHCH2CH3 t-Bu WZtfR 28 O FORMULA 34 Ph t-Bu _0- t-Bu WZdR 29 t-Bu t-Bu- D -Bu-rt —0 ^ '' -oO t-Bu WZdR 30 t-Bu WZdR 31 \ t-Bu WZdR 35 WZdR 36 t-Bu t-Bu WZdR 37 CH2 POO-CH3 t-Bu WZdR 32 CH3 ^ y — o t-Bu wz0R 38 t-Bu po ^ n-cH3 t-Bu150 429 t-Bu t-Bu -Q- ^ t-Bu ^ Q 0, / p- ° - ^ Q) -0CH3 t-Bu WZ (5R 39 t- Bu t-Bu t-Bu t ~ Bu WZtfR 40 t-Bu I t-Bu-Q ° - t-Bu-Q O t-Bu \ F / -oO CN WZtfR 42 150 429 t-Bu jH2 p- ° ^ 0- CH3 CH3HU) O CH3 t-Bu WZdR 47 OOLo l-Bu ^ \ I CH2 P-0 ^ O-CH3 CD t_Bu WZCfR 51 t-Bu FORMULA 48 t-Bu CH3 "° v t-Bu h2 / - ° ^ y CH3 ^ 0 O 't-Bu WZCiR AS CH3-0 \ ^ 3 CH2 P-OHOKH3 CH 3- CH3 WZtfR 54 MODEL 50 150 429 t-Bu t-Bu-O Q t-Bu. t-Bu \ II PO-CH2CH2OCCH3 t-Bu -Ó- ^ -md o -0-CH2CH2SCH3 WZdR 55 t-Bu WZdR 59 t-Bu t-Bu-cT)) 0 ..- Bu ^ - fi P — 0 -CH2COCH3 t-Bu WZCJR 56 t-Bu t_BUHq) —o- t-Bu. P-0-CH2CH2SCH3 t-Bu ^ O) oX 8 t-Bu WZdR 60 t-Bu -0-CH2CH2N (CH3) 2 t_Bu ^ p \ _ 0 WZdR 57 t-BuHO OT t-Bu P-0-CH2CH2P (CH3) 2 WZdR 61 t-Bu t-Bu- (Q 0, t-Bu P-0-CH2CH2SCH3 t-Bu t ¦ * - G t-Bu t-Bu WZdR 58 \ ii P-0-CH2CH2P (CH3) (Ph) t-Bu WZdR 62 150 429 t-Bu '- »- Q— \ 8 I P-0-CH2CH2P (H) (Ph ) t-Bu FORMULA 63 P-0-CH2-Ph t-Bu t-Bu CH3 "CH2 -0-CH2CH2NHCCH3" "sO — o 't-Bu WZdR 64 P OCH3 t-amyl t-amyi FORMULA 65 t-amyl "fc ± 7 t-amyl t-Bu P-0-CH2CH2P (Ph) 2 t-Bu t-Bu FORMULA 69 t-Bu t-Bu D- °. \ V-0 ~ CH2CH2Si (CH3) 3 t-Bu ^ H) & t-Bu WZdR 70 t-Bu t- * \ / P-O-CH2CH2Si (OCH3) 3 PO-CH ^ h ^ OCH ^ h ^ OCHs t-Bu WZdR 71 WZdR 67 150 429 P-O-CH2CH20CH3 t-Bu MODEL 72 t-Bu l-Bu-0— ° V PO-Ph t - ^ - o— ° t-Bu MODEL W t-Bu ch3 ~ Q— <CH2 PO-Ph CH3-0 —- o / t-Bu FORMULA? Y q ^ CH2 ^ PO-BHT OW \ i = ^ FORMULA 75 t-Bu t-Bu t-Bu PO-BHT t-Bu FORMULA 76 ' \ .PO-BHT O "MODEL 77 t-Bu t-Bu t-Bu t-Bu PO-CH3 t-Bu t-Bu t-Bu MODEL 78 P-0-CH2CH2CN t-Bu MODEL 79150429 on t-Bu r - ° \ K CH2 p-0- ^ n) ^ CH3 Dor-0 »WZdR 80 t-Bu '-Bu ^ D— °. T-Bu \" P-O-CH2PPh2 MC ch3hQ ^ -o CH2 / - ° ^ Q ^ CH3 CH3 1_J MC WZdR 83 --O FORMULA 84 t-Bu CH3 CH2, p-0- ^ Q-CH3 CH3- (C; —o Uu t-Bu WZdR 66 150 429 CH3 CH3 ^ Q ° ^ ch2 yop CH3-Q- ° t-Bu- CH3 FORMULA 87 ch3hQ) o. \ T-Bu CH3 CH-: CH2 D- ^ CH2 ch3 ^ Q — oh P-0hQ ^ CH3 CH3-O Ov t-Bu t-Bu WZdR 88 CH2 cH3- CH3 FORMULA 92 t-Bu CH3 ^ CJ ° s CH2 PO-CH3 CH3 t-Bu FORMULA 93 FORMULA 89 t-Bu c »-Q— ° \ j-bu CH2 P-0-ttP-CH3 I / f ^ ci ~ 0— t_BU WZdR 90 CH3-0 ° v H * u? H2 PO ^ P CH3-O — oX t-Bu WZdR 9 i150429 € M3P WZCJR 95 'C2H5 SP4H9 / CH-CH20) 3P MODEL 96 O No. 'Ph' FORMULA 97 CH-. / - ° -jcHh3 CH3 FORMULA 98 © (C6H50) 3P? NC ^ HgCHO? C ^ HgCH- P (OCgH5) 3 O © OH "* / 2H0O SC ^ CH-PlOC ^ _c H qh .C ^ H9C: HP-X6H5 —Z- C4HgCH-P-OH OH 6 5 OH XOC6M5-2C6H5OH OH \) H SCHEME PL

Claims (17)

1. Claims 1. A process for hydroformylating an ethylenically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a Group VIII transition metal catalyst with a phosphate ligand to form aldehydes, characterized in that the hydroformylation of the ethylene compound is carried out in the presence of a catalyst comprising a complex from rhodium complexed with carbon monoxide and a diorganophosphite ligand of formula I, in which W is an alkyl radical of 1-18 carbon atoms optionally containing one or more phenyl, cyano, halogen, nitro, trifluoromethyl, hydroxyl, amine, -COR6, where R6 is an alkyl group of 1-10 carbon or phenyl atoms, carbonyloxy, oxycarbonyl, amide, sulfonyl, sulfinyl, silyl, ether, phosphonyl, thionyl or W is an alpha-naphthyl radical, beta-naphthyl radical or Formula 6, wherein X1, X2 and Z4 each represent a hydrogen atom, an alkyl radical y, phenyl, benzyl, cyclohexyl, 1-methylcyclohexyl, cyano, halogen, nitro, trifluoromethyl, hydroxyl, amine, -COR6, where R6 is as defined above, carbonyloxy, oxycarbonyl, amide, sulfinyl, sulfonyl radicals silyl, ether, phosphonyl or thionyl, and Ar, the same or different, is an aryl radical substituted with one or more of the substituents given above for X1, X2 and Z4, Q is a divalent bridging group such as -CR1R2- or -S - in which the formulas R1 and R2 are each individually hydrogen or an alkyl radical of 1-12 carbon atoms, n is a number 0 or 1, and in the presence of the added free diorganophosphite ligand of the formula I, wherein W, Ar, Q and n are as above given meaning. 2. The method according to claim The process of claim 1, wherein the ethylenically unsaturated compound is a compound such as alpha-olefins with 2-20 carbon atoms, internal olefins with 4-20 carbon atoms, and mixtures of such internal alpha-olefins. 3. The method according to p. The process of claim 1, characterized in that the hydroformylation reactions are carried out at a temperature of about 50-120 ° C, under the total pressure of a gas mixture consisting of hydrogen, carbon oxide and an ethylenically unsaturated organic compound of about 6.87-10 -10305.00 • 10 Pa, the partial pressure of hydrogen about 103.05'103-1099.20 * 103 Pa and the partial pressure of carbon monoxide about 6.87 • 103-824.40 • 103 Pai in the presence of about 4-50 mol of diorganophosphine ligand / mol of rhodium in the environment reaction. 4. The method according to p. The process of claim 1, wherein part of the hydroformylation reaction fluid is removed from the formylation reaction zone, treated with a weakly basic ammonium resin and returned to the reaction zone. 5. The method according to p. The process of claim 4, wherein the hydroformylation reactions are carried out with continuous recycle of the catalyst-containing fluid. 6. The method according to p. The process of claim 4 or 5, characterized in that the aldehyde compound is released from the removed part of the hydroformylation reaction fluid with the aid of a weakly basic anion exchange resin. 7. The method according to p. 6. The process of claim 6, wherein the weakly basic anion exchange resin is a cross-linked H-amine polystyrene anion exchange resin of the gel or macroreticulum type. 8. The method according to p. The ligand of claim 1, wherein the rhodium-complexed diorganophosphite ligand and the free diorganophosphite ligand are separately used ligands of formula II, in which Q is a group of formula -CR1R2, where R1 and R2 are each separately hydrogen or an alkyl radical with 1-12 carbon atoms, n is 0-1, Y1, Y2, Z2 and Z3 each represent hydrogen, an alkyl radical of 1-18 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl, alicyclic and ether groups, with the proviso that the radical Y1 or Y2 has a spatial hindrance in the form of an isopropyl group or more, and W is a substituted or unsubstituted alkyl radical. 9. The method according to p. A process as claimed in claim 8, characterized in that the olefinic starting compound is butene-1, butene-2, isobutylene and an olefin mixture consisting essentially of butene-1 and butene-150 429 45 2, and the compound of formula 2 is used as the phosphorus ligand, where Q is -CH2- or -CHCH3, Y1 and Y2 are branched alkyl radicals with 3-5 carbon atoms and W is an unsubstituted alkyl radical with 1-10 carbon atoms. 10. The method according to p. The process as claimed in claim 9, characterized in that the compound of formula 2 is used, wherein Y1 and Y2 represent IIF-butyl radicals, Q is -CH2- and W is an unsubstituted alkyl radical with 1-8 carbon atoms. 11. The method according to p. 8. The process according to claim 8, characterized in that the compound of formula 2 is used in which Y1 and Y2 represent t-butyl radicals, Q is -CH2- and W is an alkyl radical substituted with a phosphonyl group of formula -CH2PO / R3 / 2, in which each R3 the same or different and individually represents an alkyl or phenyl group, one of the R3 groups may also be hydrogen. 12. The method according to p. The method of claim 11, characterized in that a compound of formula 2 is used, in which W is a radical of formula -CH2P / O / / C6H5 / 2, and the other symbols have the meaning given above. 13. The method according to p. 3. The ligand according to claim 1, characterized in that as the diorganophosphite ligand complexed with rhodium and the free diorganophosphite ligand, ligands of formulas 3 and 4 are used separately, in which Q represents a group of formula -CR1R2, in which R1 and R2 are each separately hydrogen, the radical alkyl of 1-12 carbon atoms, and n is the number O1, X ', X ", Y \ Y", Z', Z 'and Z ° each separately represent hydrogen, alkyl group with 1-18 carbon atoms, phenyl, benzyl , cyclohexyl, 1-methylcyclohexyl, hydroxyl, carbonyloxy and ether groups, provided that simultaneously at least two radicals X1 and X2 or at least two radicals Y1 and Y2 are radicals hindered in the form of an isopropyl group or more, and also with that in formula III, no more than three radicals such as X1, X2, Y1 or Y2 are hindered radicals in the form of an isopropyl group or more. 14. The method according to p. The process as claimed in claim 13, characterized in that the compound of formula 3 or 4 is used in which Q is -CH2- or -CHCH3- and Y1 and Y2 are branched chain alkyl radicals containing 3-5 carbon atoms. 15. The method according to p. The process of claim 13, wherein the olefinic starting material is butene-1, butene-2 and isobutylene, and an olefin mixture consisting essentially of butene-1 and butene-2, and a compound of formula 3 or 4 wherein Q is - CH2-, and X1, X2, Y1, Y2, Z1, Z2 and Z3 are each hydrogen, an alkyl radical of 1-8 carbon atoms, hydroxyl, carbonyloxy and ether groups. 16. The method according to p. The method of claim 15, wherein the diorganophosphite ligand is a compound of formula 12, 12a and 12b in which Q is -CH2- and n is 0 or 1. 17. A process for hydroformylation of an ethylenically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a group VIII transition metal catalyst with a phosphate ligand to form aldehydes7, characterized in that the hydroformylation of the ethylene compound is carried out in the presence of a catalyst consisting of a complex consisting of complexed with carbon monoxide and the diorganophosphite ligand of formula 5, where Q is -CH2- or -CHCH3-, each R6 is an alkyl radical of 1-10 carbon atoms, Y1 and Y2 each individually is hydrogen, a branched chain alkyl radical containing 3 - 12 carbon atoms, phenyl, benzyl, cyclohexyl and 1-methylcyclohexyl groups. W is an aryl radical of formula 6, where X1, X2 and Z4 are each hydrogen, an alkyl radical of 1-18 carbon atoms, optionally substituted radical aryl, alkaryl, aralkyl and alicyclic, cyano, halogen or ether groups, with n at least two X1 and X2, or at least two Y1 and Y2 in a given Uganda, are hindered radicals in the form of an isopropyl group or more, and with no more than three X1, X2, Y1 or Y2 being radicals having a spatial hindrance in the form of an isopropyl group or more and in the presence of an added free diorganophosphite ligand of formula 5, where W, Q, Y1, Y2, R6 have the meaning given above 150 429 (Ar) Ov I \ (a) n pow (Ar) ia) n pow Y2 FORMULA 2 ^ 4 FORMULA 1: A Z2 ^ ° \ L. Y WZdR 3 ^ CH2CH2x —NO ^ CH2CH2 FORMULA 7 / CH2- CH2 —N \ / CH2CH2x CH2CH2 / * C —CHo II * O WZdR 8 WZdR 9 OI! - N ^ C — CH2 XC — CH2 WZdR 10 WZdR 4 WZdR 11 (Qn t-C4Hg ^ P- ° -0-CH3 ¦V Uc4H9 WZdR 12 FORMULA 5 150 429 t— C4H9? -C4H9-O ° v t- < * Hg-0 ° t-C4Hg WZOR 12a CH3O CH3O t-Bu; po-CH3 t-Bu FORMULA 15 t-Bu CH3 ° - ^ 0 ° ^ rf ^ f% t_rH J \ ^ / MM— ° \ 139 l ^ n P-0 ^ Q-CH3 CH3CHO <OO ° ^ I- Bu P-0- (CH2) 17CH3 WZ0R 12b l— Bu HO HO ^ D o • ^ - © t- Bu WZCfR 13 FORMULA 16 t-Bu CH ^ O— (C) 0. CH2 P-O-CH3 / —er WZdR 17 t-: K30- ^. CH; CH3 ° -0 "t-Bu H0-O 0, HO-O, P-O-CH3 I t-Bu FORMULA U t-Bu FORMULA 18150 429] -Bu t-amyl \ / P- ° "HQ ^ ° CH3 ^ J / -O-CH3 CH3 ° -0 ° CH3 ° -0 O" t-Bu WZtfR 19 "" -O CH30 t-Bu WZtfR 20 t- Bu CH3O-O ° v CHoO - ° ^ O ^ 0CH3 P-0 ~ CH3 I P-0 CH3 ° ^ 0 ° t-Bu t-Bu FORMULA 21 WZtfR 25 t -Bu CH3 ° -— ° ^ CH30-O o '- ° ^ 0 ^ C9Hl9 CH3O CH3O t - Bu 1 p- ° ^ O ^ ocH3 t — Bu CHo— Ph FORMULA 22 FORMULA 26150 429 Ph ch3ohQ o. T-Bu t-Bu \ t-Bu- P-0- Ph WZdR 27 l-Bu t- Bu y 0 t-Bu WZ (5R 33 0. t-Bu CH3 \ F y f- ° -0 ^ CHCH2CH3 t-Bu WZtfR 28 O WZODR 34 Ph t-Bu _0- t-Bu WZdR 29 t-Bu t-Bu- D -Bu-rt — 0 ^ '' -oO t-Bu WZdR 30 t-Bu WZdR 31 \ t-Bu WZdR 35 WZdR 36 t-Bu t-Bu WZdR 37 CH2 POOC H3 t-Bu WZdR 32 CH3 ^ y — o t-Bu model 38 t-Bu po ^ n-cH3 t-Bu150 429 t-Bu t-Bu -Q- ^ t-Bu ^ Q 0, / p- ° - ^ Q) -0CH3 t-Bu WZ (5R 39 t-Bu t-Bu t-Bu t ~ Bu WZtfR 40 t-Bu I t-Bu-Q ° - t-Bu-Q O t-Bu \ F / - oO CN WZtfR 42 150 429 t-Bu jH2 p- ° ^ 0-CH3 CH3HU) O CH3 t-Bu WZdR 47 OOLo l-Bu ^ \ I CH2 P-0 ^ O-CH3 CD t_Bu WZCfR 51 t-Bu FORMULA 48 t- Bu CH3 "° v t-Bu h2 / - ° ^ y CH3 ^ 0 O 't-Bu WZCiR AS CH3-0 \ ^ 3 CH2 P-OHOKH3 CH3- CH3 WZtfR 54 FORMULA 50 150 429 t-Bu t-Bu-O Q t-Bu. t-Bu \ II PO-CH2CH2OCCH3 t-Bu -Ó- ^ -md o -0-CH2CH2SCH3 WZdR 55 t-Bu WZdR 59 t-Bu t-Bu-cT)) 0.-Bu ^ - fi P — 0 -CH2COCH3 t-Bu WZCJR 56 t-Bu t_BUHq) —o- t-Bu. P-0-CH2CH2SCH3 t-Bu ^ O) oX 8 t-Bu WZdR 60 t-Bu -0-CH2CH2N (CH3) 2 t_Bu ^ p \ _ 0 WZdR 57 t-BuHO OT t-Bu P-0-CH2CH2P (CH3) 2 WZdR 61 t-Bu t-Bu- (Q 0, t-Bu P-0-CH2CH2SCH3 t-Bu t ¦ * - G t-Bu t-Bu WZdR 58 \ ii P-0-CH2CH2P (CH3) (Ph) t-Bu WZdR 62 150 429 t-Bu '- »- Q— \ 8 I P-0-CH2CH2P (H) (Ph ) t-Bu FORMULA 63 P-0-CH2-Ph t-Bu t-Bu CH3 "CH2 -0-CH2CH2NHCCH3" "sO — o 't-Bu WZdR 64 P OCH3 t-amyl t-amyi FORMULA 65 t-amyl "fc ± 7 t-amyl t-Bu P-0-CH2CH2P (Ph) 2 t-Bu t-Bu FORMULA 69 t-Bu t-Bu D- °. \ V-0 ~ CH2CH2Si (CH3) 3 t-Bu ^ H) & t-Bu WZdR 70 t-Bu t- * \ / P-O-CH2CH2Si (OCH3) 3 PO-CH ^ h ^ OCH ^ h ^ OCHs t-Bu WZdR 71 WZdR 67 150 429 P-O-CH2CH20CH3 t-Bu FORMULA 72 t-Bu l-Bu-0— ° V PO-Ph t - ^ - o— ° t-Bu FORMULA W t-Bu ch3 ~ Q— <CH2 PO-Ph CH3-0 —- o / t-Bu FORMULA? t ^ CH2 ^ PO-BHT OW \ i = ^ FORMULA 75 t-Bu t-Bu t-Bu PO-BHT t-Bu FORMULA 76 '\ .PO-BHT O "MODEL 77 t-Bu t-Bu t-Bu t-Bu PO-CH3 t-Bu t-Bu t-Bu MODEL 78 P- O-CH2CH2CN t-Bu FORMULA 79150429 on t-Bu r— ° K CH2 p-0- ^ n) → CH3 Dor-O → WZdR 80 t-Bu '-Bu D— °. t-Bu \? P-O-CH2PPh2 MC ch3hQ ^ -o CH2 / - ° ^ Q ^ CH3 CH3 1_J MC WZdR 83 --O FORMULA 84 t-Bu CH3 CH2, p-0- ^ Q-CH3 CH3- (C; --o Uu t-Bu WZdR 66 150 429 CH3 CH3 ^ Q ° ^ ch2 yop CH3-Q- ° t-Bu- CH3 FORMULA 87 CH3hQ) o. \ t-Bu CH3 CH-: CH2 D- ^ CH2 ch3 ^ Q — oh P-0hQ ^ CH3 CH3-O Ov t-Bu t-Bu WZdR 88 CH2 cH3- CH3 FORMULA 92 t-Bu CH3 ^ CJ ° s CH2 PO-CH3 CH3 t-Bu FORMULA 93 FORMULA 89 t-Bu c »-Q— ° \ j-bu CH2 P-0-ttP-CH3 I / f ^ ci ~ 0— t_BU WZdR 90 CH3-0 ° v H * u? H2 PO ^ P CH3-O — oX t-Bu WZdR 9 i150429 € M3P WZCJR 95 'C2H5 SP4H9 / CH-CH20) 3P MODEL 96 O Item' Ph 'MODEL 97 CH-. / - ° -jcHh3 CH3 FORMULA 98 © (C6H50) 3P n-C ^ HgCHO? C ^ HgCH- P (OCgH5) 3 O © OH "* / 2H0O SC ^ CH-PlOC ^ _c H qh. C ^ H9C: HP-X6H5 —Z- C4HgCH-P-OH OH 6 5 OH XOC6M5-2C6H5OH OH \ H SCHEMAT PL