Title of Invention

PROCESS FOR THE MANUFACTURE OF CHROMAN DERIVATIVES, ESPECIALLY ALPHA-TOCOPHEROL AND ALKANOATES THEREOF

Abstract

The present invention relates to novel processes for the manufacture of derivatives such as alpha-tocopherol (TCP) and alkanoates thereof, especially alpha-tocopheryl acetate (TCPA), whereby at least one step of the processes is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, preferably at an absolute pressure of at least 1.1 bar. As starting materials for the manufacture of TCP and its alkanoates either a mixture of 2,3,5-trimethylhydroquinone (TMHQ) or 2,3,6-trimethylhydroquinone-l-alkanoate (TMHQA) and a compound selected from the group consisting of phytol (PH), isophytol (IP) and (iso)phytol derivatives or 2-phytyl-3,5,6-trimethyl-hydroquinone (PTMHQ)/3- phytyl-2,5,6-trimethylhydroquinone-1 -alkanoate (PTMHQA) and/or an isomer thereof are used. Suitable Lewis acids are indium(lll) salts and scandium(lll) salts. Suitable acid mixtures are iron/iron(ll) chloride/hydrogen chloride and zinc(ll) chloride/hydrogen chloride.

Full Text

Process for the manufacture of chroman derivatives, especially a-toco-pherol and aUca- noates thereof The present invention relates to a novel process for the manufacture'of chroman derivatives, especially for the manufacture of a-tocopherol (TCP) and alkanoates (TCPA) thereof such as a-tocopheryl acetate (TCP Ac), whereby at least one step of the process is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted -acid as the catalyst under pressure. Preferably the absolute pressure of the reaction is at least 1.1 bar, more preferably it is from about 1.1 bar to about 20.0 bar, even more preferably it is from about 1.1 bar to about 6.0 bar. As starting materials for the manufacture of TCP and its alkanoates either a mixture of 2,3,5-trimethylhydroquinone (TMHQ) or 2,3,6-trimethylhydroquinone-l-allcanoate ! l (TMHQA) and a compound selected from the group consisting of phytol (PH), isophytol (IP) and (iso)phytol .derivatives, or the "open ring" compound 2-phyryl-3,5,6-trimethyl-hydroquinone (PTMHQ), a 3-phvryl-2,5,6-1rimet;hylhydroquinone-l-alkanoate (PTMHQA) and/or an isomer thereof are used. As is known, (all-rac)-a-tocopherol (or as it has mostly been denoted in the prior art, "d,l-K-tocopheroI") is a mixture of four diastereomeric pairs of enantiomers of 2,5,7,S-tetra-me&y]-2-(4',S\12t-trimetliyl-tridec3''l)-6-chrornanol (a-tocopherol), which is the biologically most active and industrially most important member of the vitamin E group. Many processes for the manufacture of "d,l-o^tocopheror (referred to as such in the literature reviewed hereinafter) and its acetate by the reaction ofTMHQ/2,3,6-trimethyl-hydroquinone-1 -acetate (TMHQAc) with IP or PH in the presence of a catalyst or catalyst system and in a solvent or solvent system are described in the following selected literature. The manufacture of Oi-tocopherol hy the reaction of TMHQ with PH or phytyl bromide in the presence of anhydrous ZnCl2 is e.g. described in US 2,411,967. According to DE 196 54 038 Al TMHQ is reacted with PH or ff to Oi-tocopherol and its acetate in the presence of ZnCIa and a proton donor, whereby-in the process of US 3,708,505 a combined acid condensation agent comprising a Lewis acid such as ZnQa -and at least one strong acid such as p-toluene sulfonic acid and sodium bisulfate is used as the catalyst. In EP-A 0 100 471 the reaction of TMHQ with ff or PH in the presence of a Lewis acid, e.g. ZnCli, BF3 or Aids, a strong acid, e.g. HC1, and an amine salt as the catalyst system is described. In the processes of DE-OS 26 06 830 and US 4,191,692 the ff or PH is pre-. treated with ammonia or an amine before the reaction with TMHQ in the presence of and an acid is effected. In the processes of DE-OS 21 60 103 as well as US 3,789,086 compounds of the following formula (Figure Remove) wherein X is hydrogen, alkanoyl or aroyl, and R1, R2 and R3 are individually hydrogen or methyl, are reacted with compounds of the following formulae (Figure Remove)wherein Y is ~CH2-CH(CH3)- or -CH=C(CH3)- and A is halogen, hydroxy, etherified hydroxy or esterified hydroxy in the presence of HC1 and Fe 'and/or FeC^ as the catalyst to obtain e.g. otocopherol. According to EP-A 0 694 541 TMHQ:and IP, PH or a PH derivative are reacted in the presence of a mineral acid, a Lewis acid, an acidic ion exchange resin or a triflate, nitrate or sulfate of Sc, Y or a lanthanide element as the catalyst. The use of Sc(m) triflate as catalyst for the condensation of TMHQ with IP is also described in Bull. Chem. Soc. Jpn. 1995,68,3569-3571. TCP can be converted into its acetate, succinate and further known application forms by standard methods, e. g. as described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A27,5th edition, pages 484 to 485, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1996. In contrast to TCP which is labile against oxidative conditions, the esters (TCP A) are more stable and more convenient to handle. The object of the present invention is to provide a process for the manufacture of-chroman derivatives such as tocols and tocopherols and of their alkanoates, especially of a-toco-pherol and its alkanoates, with high selectivities and yields. According to the present invention this object is achieved by the use of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, preferably at an absolute pressure of at least"!. 1 bar, more preferably at an absolute pressure of from about 1.1 bar to about 20.0 bar, even more preferably at an absolute pressure of from about 1.1 bar to about 6.0 bar. It has been surprisingly found that pressure has a positive effect on s.- • .S ' • - the condensation reaction of phenols such as TMHQ or TMHQA with compounds such as IP, PH or a derivative thereof and on the ring closure reaction of PTMHQ or PTMHQA and/or isomers thereof to produce a-tocopherol as well as on the acylation of tocols and tocopherols. Therefore, in one aspect, the present invention is concerned with a process for the manufacture of 2-alkenyl-3,5,6-trimethylhydroquinone (formula I with n = 0 to 3; R1 = hydrogen) and 3-aUcenyl-2,556-trimethylhydroquinone 1-alkanoate (formula I with n = 0 to 3; R1 = acetyl, propionyl, pivaloyl, HC^C-CHj-CHr-CO, nicotinoyl or benzo}'!), most preferably a process for the manufacture of 2-phytyl-3,5,6-trirnethylhydroquinone (formula I with P.1 - hydrogen and n = 3) and 3-phyt\d-2,5,6-tiniethylhydroquinone-l-alicanoates (formula I with R1 = acetyl propionyl, pivaloyl,-HO2C-C^r-CHr-CO, nicotinoyl or "benzoyl and n -3), OH (I) (Figure Remove) by reacting 2,3,5-trimethylhydroquinone (formula IE with R1 = hydrogen) and 2,3,6-trimethylhydroquinone-1-alkanoate (formula n with R1 = acetyl, propionyl, pivaloyl, H02C-CH2-CH2-CO, nicotinoyl or benzoyl), respectively, (Figure Remove) whereby R1 is hydrogen, acetyl, propionyl. pivaloyl, HOsC-CHr-CHr-CO, nicotinoyl or benzoyl, R2 is hydroxy, acetyloxy, benzoyloxy or halogen, and n is an integer from 0 to 3, and whereby the reaction is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, preferably at an absolute pressure of-at least 1.1 bar, more preferably at an absolute pressure of from about 1.1 bar to about 20.0 bar, even more preferably at an absolute pressure of from about 1.1 bar to about 6.0 bar. This process is referred to as .PROCESS 1 hereinafter. Cpncerninp the substituent R1: preferably it is hydrogen or acetyl, more preferably it is hydrogen. Concerning the substituent R2: preferably R2 is hydroxy, acetyloxy, benzoyloxy, chlorine or bromine, more preferably R2 is hydroxy, acetyloxy or chlorine, most preferably R2 is hydroxy. Concerning the integer n: preferably n is 3. While in PROCESS 1 of the present invention the production of (all-rac)-2-alkeriyl-355,6-trimethylhydroquinone, e.g. (all-7-ac)-PTMHQ, or (all-rac)-3-alkenyl-2,5,6-trimethyl-hydroquinone 1-alkanoate, e.g. (all-7-cc)-PTMHQA, especially (aU-rac)-3-phytyl-2,5,6-tri-' methylhydroquinone-1-acetate (PTMHQAc), is preferred, the invention is not limited to the production of that particular isomeric form and other isomeric forms can be obtained by using e.g. phytol (formula IV with R2 = OH and n = 3), isophytol (formula ffi with R2 = OH and n = 3) or a derivative thereof as the starting material in the appropriate isomeric form. Thus, (J^)-PTMHQ or (R^-TTMEQA will be obtained e.g. when using (_RJt)~ phytol, (lrRrR)-isophytol, (iS,l?y/?)-isophytol or (AS',^rR)-isophytol or an appropriate , -. • ... •'•>•: s •- «• (iso)phytol derivative. PROCESS 1 is also applicable for the allcenylation of phenols comprising 0 to 4 methyl groups, a total of 1 to 3 hydroxy groups and at least one unsubstituted position, whereby the unsubstituted position is ortho to a hydroxy group. Therefore, a further object of the present invention is a process for the alkenylation of phenols comprising 0 to 4 methyl groups, a total of 1 to 3 hydroxy groups and at least one unsubstituted position, whereby the unsubstituted position is ortho to a hydroxy group, with a compound of the formula IE and/or IV in an organic solvent (Figure Remove) with R2 and n having the same meanings and preferences as above, and whereby the reaction is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, preferably at an absolute pressure of at least 1.1 bar, more preferably at an absolute pressure of from about 1.1 bar to about 20.0 bar, even more preferably at an absolute pressure of from about 1.1 bar to about 6.0 bar. This process is referred to as PROCESS 1A hereinafter. Concerning the phenols used in PROCESS 1A as the starting material: Especially suitable phenols have the following formula Ea (Figure Remove) with R3 being hydrogen, acetyl, propionyl, pivaloyl, HC^C-CH^-CBb-CO, nicotinoyl or benzoyl, and X1, X2 and X3 being independently from each other hydrogen or methyl, with the proviso that R3 is only acetyl, propionyl, pivaloyl, H02C-CH2-CH2-CO, nicotinoyl or benzoyl, if X1, X2 and X3 are all methyl; i.e. hydroquinone, 2-memylhydroquinone, 2,3-di-methylhydroquinone, 2,5-dimethylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone and 2,3,6-trimethylhydroquinone-l-alkanoates. Preferred from this group are 2,3,5-rrimethylhydroquinone and 2,3,6-rrimethylhydroquinone-l-alkanoates, more preferred are 2,3,5-trimethylhydroqiiinone and 2,3,6-triniethylhydroqiunone-l-acetate. the most preferred is 2,3,5-trimethylhydroqumone. In another aspect, the present invention is concerned with a process for the manufacture of compounds of the formula VH, preferably a-tocopherol (formula VII with R1 = hydrogen and n = 3) and its alkanoates (formula VII with R1 = acetyl, propionyl, pivaloyl, , nicotinoyl or benzoyl and n = 3) (Figure Remove) by a) (STEP a) optionally reacting 2,3,5-trimemylhydroquinone (formula n with R1 = hydrogen) and 23,6-trimethylhydroquinone 1-alkanoate (formula n with R1 = aceryl, propionyl, pivaloyl, HOsC-CH^-CH/r-CO, nicotinoyl or benzoyl), respectively, with a compound of the formula in and/or IV in an organic solvent (Figure Remove) with R1, R2 and n having the same meanings and preferences as above, and b) (STEP b) submitting in an organic solvent a 2-aikeriyl-3,5,6-trimethylhydroqunone (formula I with R1 = hydrogen), preferably 2-phytyl-3,5,6-trimethyIhydroqunione formula I with R = hydrogen and n ~ 3), a 3-aHcenyl-2,5,6-trimethylhydroquinone 1-alkanoate (formula-1 with R1 = acetyl, propionyl, pivaloyl, nicotinoyl or benzoyl), preferably 3-phytyl-2,5,6-trimethylhydroquinone 1-alkanoate (formula I with R1 = acetyl, propionyl, pivaloyl, H02C-CH2-CH2-CO, nicotinoyl or benzoyl and n = 3) and optionally one or more double bond isomers thereof, all obtainable by step a), (Figure Remove) to ring closure to form chroman derivatives VH, preferably a-tocopherol (formula VII with R1 = hydrogen and n - 3) or its alkanoate (formula VH with R1 = acetyl, propionyl, pivaloyl, H02C-CHr-CH2-CO, nicotinoyl or benzoyl and n = 3), whereby at least one of the steps a) and b) is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, preferably at an absolute pressure of at least 1.1 bar, more preferably at an absolute pressure of from about 1.1 bar to about 20.0 bar, even more preferably at an absolute pressure of from about 1.1 bar to about 6.0 bar. This process is referred to in the following as PROCESS 2. Depending on the activity of the catalyst and the reaction conditions, the reaction of compounds of the formula E with compounds of the formula m and/or IV proceeds to the final product of the formula VE, preferably a-tocopherol and its alkanoate, so that the compounds of the formula I such as PTMHQ (formula I with R1 = hydrogen and n = 3) and PTMHQA (formula I with R1 = acetyl, propionyl, pivaloyl, H02C-CHr-CH2-CO, nicotinoyl or benzoyl and n = 3) are not isolated. Therefore, a further aspect of the present invention is the manufacture of chroman derivatives YE such as a-tocopherol (formula VE with R1 = hydrogen and n = 3) and its alka-noates (formula VE with R1 = acetyl, propionyl, pivaloyl, HOsC-CHz-CHa-CO. nicotinoyl or benzoyl and n = 3) (Figure Remove) by reacting 2,3,5-trimethylhydroquinone (formula n with R1 = hydrogen) and 2,3,6-trimethylhydroquinone 1-alkanoate (formula II with R1 = acetyl, propionyl, pivaloyl, HOjC-CHr-CBr-CO, nicotinoyl or benzoyl), respectively, (Figure Remove) with a compound of tie formula HI and/or a IV in an organic solvent (Figure Remove) , whereby the reaction is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, preferably at an absolute pressure of at least 1.1 bar, more preferably at an absolute pressure of from about 1.1 bar to about 20.0 bar, even more preferably at an absolute pressure of from about 1.1 bar to about 6.0 bar. This process is referred to in the following as PROCESS 3. As starting material in PROCESS 3 also a compound of the formula IX instead of a com-poimd of the formula IH andVor TV (Figure Remove) are obtained. R1, R2 and n have the same meanings and preferences as above. To this process it will be referred to in the following as PROCESS 4. While in the PROCESSES 2 and 3 of the present invention the production of (all-rac)-chroman derivatives such as (all-7- In an especially preferred embodiment of the invention TMHQ is reacted with PH (formula TV with R2 = OH and n = 3) and/or IP (formula IE with R2 = OH and n = 3), preferably with IP. to a-tocophero! (formula YE with R1 = hydrogen and n = 3), whereby as intermediates compounds of the formula V (see below) and VI (see below) such as 2-phytyl-3.5,6-trimethylhydroquinone (formuls! with R' = hydrogen and n *= 3; as main component), 2-(3,7,1 l,15-tetramemyl-hexadec-3-enyl)-3.5,6-trimethy3hydroquinone (formula Va with R1 "? hydrogen) and 2-[3-(4,S J2-trimethyl-tridecyr)-but-3-enyl]^3,5,6-trnnethy]hydroquinone (formula Via with R1 — hydrogen) are formed. (Figure Remove) PROCESSES 2 and 3 can also be carried out by using phenols of the formula Ha, whereby, beside a-tocopherol and its alkanoates, e.g. other tocols (formula VHa with n = 3) and to-copherols (formula Vila with n = 3) can be obtained. (Figure Remove) Therefore, in another aspect, the present invention is concerned with a process for the manufacture of compounds of the formula Vila by a) (STEP a) optionally reacting a compound of the formula Ha (Figure Remove) with a compound of the formula lH and/or IV in an organic solvent with R2, R3, n, X1, X2 and X3 having the same meanings and preferences as above, and b) (STEP b) submitting in an organic solvent a compound of the formula la and optionally one or more double bond isomers thereof, all obtainable by step a), to ring closure to form a compound of the formula Vila, (Figure Remove) X whereby at least one of the steps a) and b) is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, preferably at an absolute pressure of at least 1 .Ibar, more preferably at an'absolute pressure of from about 1.1 bar to about 20.0 bar, even more preferably-at an absolute pressure of from abou 1.1 bar to about 6.0 bar. To this process it will be referred to in the following as PROCESS 2A. Depending on the activity of the catalyst and the reaction conditions, step a of PROCESS 2A can also proceed to the final products, the compounds of the formula Vila, so that the compounds of the formula la are not isolated. Therefore, a further aspect of the present invention is the manufacture of a compound of the formula Vila (Figure Remove) with R2, R3, n, X1, X2 and X3 having the same meanings and preferences as above, whereby the reaction is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, preferably at an absolute pressure of at least 1.1 bar. more preferably at an absolute pressure of from about 1.1 bar to about 20.0 bar, even more preferably at an absolute pressure of from about 1.1 bar to about 6.0 bar. To this process it will be referred to in the following as PROCESS 3A. In still another aspect the invention relates to a process for the manufacture of compounds of the formula VIEId (if n = 3: tocyl alkanoates and tocopheryl alkanoates), especially a-tocopheryl alkanoates (formula Vmd with n = 3, X]= X2 = X3 = methyl), (Figure Remove) by reacting a compound of the formula Vlld (if n = 3: a tocol or tocopherol), especially a-tocopherol (formula VHd with n = 3, X1 = X2 = X3 = methyl), obtained according to the process of the present invention, (Figure Remove) with an acylating agent. In a preferred embodiment the reaction is carried out in the presence of a Lewis acid as the catalyst. In another preferred embodiment the reaction is carried ourat reduced-pressure^preferably at an absolute pressure of below 0.9 bar, or under pressure, preferably at an absolute pressure of at least 1.1 bar (in the following referred to as PROCESS 5). Concerning the svmboLn: it is an integer from 0 to 3. rl ,r2 Concerning the symbols X VX and X_: they have the same meanings as given above. Concerning jhe substituent R: it is selected from the group consisting of acetyl., propionyl, pivaloyl, H02C-CH2-CH:-CO, nicotmoyl or benzoyl; preferably R is H02C-CH2-CH2-CO or acetyl, more preferably R is acetyl. In a preferred aspect the invention relates to a process for the manufacture of compounds of the formula Villa, preferably of compounds of the formula VUla with n = 3 (tocyl alka-noates and tocopheryl alkanoates), more preferably of a-tocopheryl alkanoates (formula with n = 3), (Figure Remove) by reacting a compound of the formula VIIc, preferably a compound of the formula "VHc with n = 3 (a tocol or tocopherol), more preferably a-tocopherol (formula VHb with n = 3), wrth'Jari'acylating agent~cn~a"racterizedin thatlhrfeactioiiis carried -dutin -the presence of a Lewis acid as the catalyst at reduced pressure, preferably at an absolute pressure of below 0.9 bar, pr under pressure, preferably at an absolute pressure of at least 1.1 bar (in the following referred to as PROCESS 5A). Concerning the symbols n, X , X and X : they have the same meanings as given above. Concerning the substituent R: it is selected from the group consisting of acetyl, propionyl, pivaloyl, H02C-CH:-CH;~CO, nicotinoyl or benzoyl; preferably R is H02C-CH2-CK2-CO or acetyl. more preferably R is acetyl. [n the same way as compounds of the formula Vffl and VHIa are manufactured compounds :>f the formula X with R1 being acetyl, propionyl, pivaloyl, H02C-CH2-CH2-CO, nicoti-noyl or benzoyl, and n being an integer from 0 to 3, (Figure Remove) (X) can also be manufactured by reacting a compound of the formula X with R1 being hydrogen and n having the same meaning as above with an appropriate acylating agent in the presence of a Lewis acid as the catalyst at reduced pressure, preferably at an absolute pressure of below 0.9 bar, or under pressure, preferably at an absolute pressure of at least 1.1 bar. To this process, which is also an object of the present invention, it will be referred to as PROCESS SB in the following. While in a preferred embodiment of PROCESS 5 A of the present invention chroman alka-noates of the formula VEIa such as (all-rflc)-TCPA (formula Vm with n = 3; see above), especially (all-rac)-TCPAc (formula V3H with n = 3 and R = acetyl) is produced, the invention is not limited to the production of that particular isomeric form and other isomeric 'forms cam Be obtained 'By e'.'g'. us'rhg'TCP (formula VDft^urn=3)'aS'tue starting material in the appropriate isomeric form. Thus, e.g. (R,R,R)-1CP A/TCP Ac will be obtained when using (R,R,R)-1CP as starting material, since no epimerization occurs at reaction temperatures below 120°C. The same applies for the other compounds of the formula \TIc used as starting materials such as e.g. tocols and tocopherols, if n = 3. In a preferred embodiment the (all-7-ac)-a-tocopherol (formula VHb with n = 3) obtained by PROCESS 2 or 3 is acetylated after removal of the solvent without further purification with acetic anhydride and with total conversion, if PROCESS 2 or 3 is carried out in the presence of a Lewis acid as the catalyst. No additional catalyst needs to be used as the catalyst (Lewis acid) is still present from the reaction before. Furthermore, it is a special advantage that the reaction mixture of the manufacture of e.g. (all-rac)-a-tocopherol can vantage that the reaction mixture of the manufacture of e.g. (all-rflc)-a-tocopherol can be acetylated at the reaction temperature the mixture already has. When indium(Er) salts are used as the catalysts, the acetylation even proceeds at room temperature in a short reaction time (up to 10 minutes). After acetylation (all-7-Qc)-a-tocopheryl acetate was isolated in excellent yield [>99.5% based on (all-7'ac)-a-tocopherol]. Lewis acids and mixtures of Lewis acids with Bronsted acids Concerning the Lewis acids and/or mixtures of Lewis acids with Bronsted acids used as the catalyst underpressure in all PROCESSES 1 to 5B: In principle all Lewis acids and mixtures of Lewis acids with Bronsted acids known to the person skilled in the art as catalysts for the > condensation reaction of TMHQ or TMHQA with IP, PH or derivatives thereof can be used. Suitable catalysts are e.g. bortrifluoride (BF3), a mixture of boric acid (especially orthoboric acid) and oxalic acid, triflateE and het-erowolfram acids. Preferred are Lewis acids, where the radius of the metal cation varies from about 73 pm to about 90 pm, preferably from about 73 pm to about 82 pm, such as the radius of Fe2+ (0.74 A), Zn2+ (0.74 A), In3+ (0.81 A) and Sc3+ (0.73 A). Especially suitable Lewis acids are indium(DI) salts such as indium(ni) halides, indiumQII) trifluoromethanesulfonate (= triflate) pn(SO3CF3)3; In(OTf)3] and indium(IH) e,J7is(trifLu,oromethanesulfcmarnide)-[In((NSO2GE3-)3)3; In(NTf2)3]^ scandiurn(Iir) salts such as those described on page 5, line 14 to 21 in combination with page 6, line 23 to page 7, line 33 ofEP 0 658552 Al, e.g. scandium(ni) fluorosulfonate [Sc(SO3F)3], scandiumQH) triflate [Sc(OTf)3] and scandium(in) fluorobenzenesulfonate [Sc(SO3C6H4F)3]; scan-dium(EI) bis(trifluoromethanesulfonamide) [Sc(NTf2)3], scandium(in) nitrate [Sc(NO3)3], scandium(ni) sulfate [Sc2(S04)3] and zinc(IT) bis(trifluoromethanesulfonamide) [Zn(NTf2)2]. More preferred are lnCi3. In(OTf}3 and Sc(OTf)3, whereby InCl3 is the most preferred one. The indium and scandium salts InCl3. In(OTf)3 and Sc(QTf)3 are known compounds which are commercially available, InCh e.g. iron: Fluka (No. 57 100), In(OTf)3 and So(OTf}3 e.g. from Aldrich (No, 442 151 and 418 218). They can be used ir. solid form, anhydrous or hydratsd (of which lnCl3-4 H^O is an example), as well as in solution or in suspension. For ROCESS 1 and 2 the catalyst is preferably dissolved or suspended in water. The concentration of such an aqueous solution is not critical; Furthermore, all the Lewis acids cited above tolerate acetic anhydride and other acylating agents as well as protic solvents such as acetic acid, methanol, ethanol and water. After the termination of the reaction the Lewis acids used as the catalysts can be recycled. Especially suitable mixtures of Lewis acids with Bronsted acids are the following systems: zinc(II) compounds/hydrochloric acid, zincQI) compounds (preferably ZnCl2)/gaseous HCI and Fe(H) chloride/gaseous HCI. The'Fe(II) chloride can be prepared in situ by the reaction of Fe with HC1, which therefore presents an equivalent system to the system Fe(II) chloride/gaseous HCI. Suitable zinc(II) compounds are zinc(IT) salts such as ZnCk, ZnBr^ as well as all zinc(II) compounds which form ZnCl? under the reaction conditions, e.g. ZnO. If the system ZnCk/hydrochloric acid or ZnClj/gaseous HCI is used, it is preferred to carry out the reaction in the presence of an arnine such as disclosed in the last paragraph onpage 4 and the first paragraph on page 5 of EP 0 100 471 Al, which is hereby incorporated by reference, or in the presence of an ammonium salt Alternatively the reaction is preferably carried out by using the compound of the formula HI or TV such as IP or PH having been pretreated with an arnine or NEb as described in DE-OS 26 06 830. ^Manufacture of the starting materials The starting material TMHQAc may be obtained e.g. by selective hydrolysis of 2,3,5-trimethylhydroquinone diacetate as described in EP-A1 239 045. 2,3,5-Trimethylhydro-quinone diacetate can be prepared e.g. by the acid catalyzed rearrangement of ketoiso-phorone in the presence of acetic anhydride or another acetylation agent as described in EP-A 0 850 910, EP-A 0 916 642, EP-A 0 952 137 or EP-A 1 028 103. The (iso)phytyl compounds can be produced by conventional processes known to the person skilled in the art. Phytol and its derivatives represented by the formula IV with n = 3 can be used as E/Z-mixture as well as in pure E- or pure Z-form. Preferred is the use of phytol and its derivatives represented by the formula IV as E/Z-rnixtures. The most preferred starting material selected from the (isc)phytyi compounds is IP. Of course any other appropriate isomeric form of the (iso)phytol derivatives can also be used, (j^-phytol, (R,RJl)-isophytol, (SA^-isophytol or (AS^^-isophytol or an appropriate (iso)phytol derivative e.g. can be used to obtain (J?,£)-PTMHQ/(£,£)-PTMHQA or , if TMHQ/TMHQA is used as the other component. The other (di)(metliyl)hydroquinones and compounds of the formula TTT and IV with n being 0, 1 or 2 can be prepared by processes known to the person skilled in the art. PROCESS 1, STEP a of PROCESS 2. STEP a of PROCESS 2a As will be readily apparent, the use of the compound of the formula II with R1 = H (= TMHQ; = formula Ila with X1, X2 and X3 = methyl and R3 = hydrogen) as a reactant in this process of the present invention will result in the production of a compound of the formula I with R1 = H such as PTMHQ (n = 3) while, when using a compound of the foimula II with R1 = acetyl, propionyl, pivaloyl, HOsC—CBb—CHj—CO, nicotinoyl or benzoyl (= TMHQA), especially TMHQAc, the respective compound of the formula I with R1 = acetyl, propionyl, pivaloyl., HOjC-CHj-CHs-CO, nicotinoyl or benzoyl such as PTMHQA/PTMHQAc (n = 3) will be obtained. If TMHQ/TMHQA is reacted with a compound of the formula El and/or IV with n being 3 in both formulas, minor amounts of the isomers of PTMHQ/PTMHQA, (Z)- or(£)-2-.(3,7,1 l?l_5-tetramethyl-hexadec-3-enyl)-3,5,6-1iimethylhydroquinone (formula Va with R1 = hydrogen; see above)/(Z)- or(£)-3-(3,7,ll,15-tetramethyl-hexadec-3-enyI)-2,5,6-tri-methylhydroquinone-l-alkanoate (formulaVa with R1 = acetyl, propionyl, pivaloyl, HO2C-CH2-CH2-CO, nicotinoyl or benzoyl; see above) and/or 2-[3-(4, 8,12-trimethyl-tridecyl)-but-3-enyl]-3,5,6-trimethylhydroquinone (formula Via with R1 = hydrogen; see above)/3-[3-(4, 8,12-trimethyl-tridecyl)-but-3-enyl]-255,6-trimethylhydroquinone-l-alkanoate (formula Via with R' = acetyl, propionyl, pivaloyl, HOiC—CE^-CHa-CO, nicotinoyl or benzoyl; see above) may be formed as by-products in PROCESS 1 as well as in STEP a of PROCESS 2 ar,ci 2A. If other compounds of the formula ffl and/or IV are used where n = 0. 1 or 2, also minor amounts of compounds of the formula V and VI may be formed as byproducts. (Figure Remove) PTMHQ/PTMHQA and their isomers represented by the formulae Va and "Via (see above; are intermediates for the production of a-tocopherol or its alkanoates (final products). Depending on the activity of the catalyst and the reaction conditions, the reaction proceeds to the final product (steps a and b of PROCESS 2) or is slowly enough so that these intermediates can be isolated (only step a of PROCESS 2 is performed). The same applies for the steps a and b of PROCESS 2a. In.a preferred embodiment of PROCESS 1 and PROCESS" 2 TMHQ is reacted with PH and/or IP, more preferably with IP. Conveniently the reaction is carried out under an inert gas atmosphere, preferably gaseous nitrogen or argon. The reaction is preferably carried out at an absolute pressure of at least 1.1 bar, more preferably at an absolute pressure of from about 1.1 to about 20.0 bar, even more preferably at an absolute pressure of from about 1.1 bar to about 6.0 bar, even more, more preferably at an absolute pressure of from about 1.7 to about 5.1 bar, most preferably at an absolute pressure of from about 2,0 to about 3.6 bar. The reaction temperature depends on the applied pressure and solvent because the reaction is carried out under reflux. Therefore, the reaction temperature is conveniently iron: about90°C to about 170'C, preferably from about 900C'to about 160°C, more preferably from about 112°C to about 160°C and most preferably from about 125 to about 150°C. Suitable organic solvents are aprotic non-polar organic solvents such as aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic hydrocarbons; halogenated aromatic hydrocarbons and mixtures thereof. Preferred examples of aliphatic hydrocarbons are Linear, branched or cyclic Cs- to C\s-alkanes. Particularly preferred are linear, branched or cyclic Ce- to Cjo-alkanes, especially preferred are hexane, heptane, octane and cyclohexane or mixtures thereof. Preferred examples of halogenated aliphatic hydrocarbons are mono- or polyhalogenated linear, branched or cyclic Cr to Ci5-alkanes. Especially preferred examples are mono- or polychlorinated or -brominated linear, branched or cyclic Cr to Cjs-alkanes. More preferred are mono- or polychlorinated linear, branched or cyclic d- to Cis-alkanes. Most preferred are 1,1,1-trichloroethane, 1,2-dichloroethane, methylene chloride and-methylene bromide. Preferred examples of aromatic hydrocarbons are benzene, toluene, o-, m- and p-xylene, 1,2,3-trimethylbenzene, mesitylene, pseudocumene, naphthalene and mixtures thereof, particularly preferred is toluene. Preferred examples of halogenated aromatic hydrocarbons are mono-or polyhalogenated benzene. Especially preferred are chlorobenzene, 1,2-dichlorobenzene, 1,3-dichloro-benzene and 1,4-dichlorobenzene. The most preferred non-polar solvents differ from catalyst to catalyst: If InCl3 is used as the catalyst, toluene and heptane are the preferred solvents; especially preferred is heptane. If Sc(OTfb is used as the catalyst, the most preferred solvent is toluene. If the catalyst system Fe (FeCl2)/HCl(g) ("(g)" = gaseous) is used, the most preferred solvent is also toluene. If the system ZnCk/hydrochioric acid or ZnCl2-/HCl(E) ("g" = gaseous) is used, it is more preferred to carry out process 1 or step a) of process 2/2a in the presence of an arnine such as disclosed in the last paragraph on page 4 and the first paragraph on page 5 of EP 0 100 471 Al, which is hereby incorporated by reference. The process can also be carried out by pretreating the compound of the formula DI or TV such as -IP or PH with an anoine or NH3 as described in DE-OS 26 06 830. If an arnine is present in an amount of about 0.05 to about 5;0 weight%, preferably of about 0.1 to about 2.0 weight% - based on the weight of the compound HI or TV, whichever is employed, the most preferred solvent for carrying out the reaction with the Zn(Tf) catalyst system is hexane. If no amine is present, the most preferred solvent for carrying out the reaction with the Zn(IT) catalyst system is heptane. The molar ratio of the compound of the formula H or Ila (most preferred: TMHQ or • TMHQA(c)) to a compound of the formula m or IV, whichever is employed, in the reaction mixture conveniently varies from about 0.95 : 1 to about 1 : 1.1, preferably from about 1 :1.01 to about 1 : 1.05. The amount of the aprotic non-polar organic solvent used is conveniently from about 0.1 ml to about 6.0 ml, preferably from about 0.15 ml to about 3.0 ml, based on 1 mmol of the compound of the formula Tfl or IV, whichever is employed. The relative amount of catalyst, based on compound HI or IV, whichever is employed, is dependent on the catalyst system used and the reactants. Conveniently the relative amount of-the catalyst based on compound HI or IV, whichever is employed, Is" at least O'.Ol mol%. Generally the relative amount of catalyst varies from about 0.01 to about 30 mol%. The optimal relative amount of the catalyst is different from catalyst to catalyst and also depends on the reactants: If InClj is used as the catalyst, it may be preferably present e.g. in a relative amount of from about 0.1 mol% to about 2.5 mol%, especially preferable in a relative amount of from about 0.1 mol% to about 2.0 mol%, more preferably in a relative amount of from about 0.1 to about 1.0 mol%, even more preferably in a relative amount of from about 0.1 to about 0.5 mol%, based on compound El or IV, whichever is employed. If Sc(OTf)3 is used as the catalyst, it may be preferably present in a relative amount of from about 0.05 mol% to about 2.0 mol%, preferably in a relative amount of from about 0.075 to about 1.5 mol%, more preferably in £ relative amount of from about 0.1 to about 1.0 mol%. based or, compound in or IV, whichever is employed. If Fe and/or FeCl; rn combination with HC1 is used as the catalyst, it may be present in an amount as described e.g. in DE - OS 21 60 103 (page 5, end of second paragraph and -claim 9) and in US 3,789,086 (column 3, lines 27 - 60). If Zn(II) and/or ZnCla is used as the catalyst^ it may be present in an amount as described e.g. in the examples 1 to 12 of US 2,411,967, in US 3,708,505 (page 1, right column, lines 26 - 44), in DE - OS 19654 038 (page 2, lines 55-63; page 3, lines 4- 6; page 3, line 60 to page 4, line 19; page 4, line 29 - 38), in EP-A 0 100 471 (page 7, lines 19 - 24), in DE -OS 26 06 830 (page 4, last two lines to page 5, first two paragraphs), in US 4,191, 692 (second column, lines 49 — 62). In this context the expression "amount of catalyst" is to be understood as referring to the weight of pure Lewis acid or pure Bronsted acid present, even though the catalyst may be impure, in the form of an adduct with a solvent and/or a solution/suspension. Ife'relative amount of the Bronsted acid depends also on the Lewis acid used and can be chosen accordingly. The reaction can be carried out batchwise or continuously, and in general operationally in a very simple manner, for example (i) by adding the compound of the formula HI or FV — as such or dissolved in the solvent, preferably as such - portionwise or continuously to a mixture of the Lewis acid, the compound of the formula Ha/H (preferred: TMHQ or TMHQA; most preferred: TMHQ or TMHQ Ac) and me solvent If_a catalyst^system cpnsisjjng,of a. . Lewis acid and a Bronsted acid is employed, the Bronsted acid is added continuously or batchwise, preferably continuously, to the mixture of the Lewis acid, the compound of the formula Ea/H (most preferred: TMHQ or TMHQA(c)) and the solvent. It is also possible (ii) to add subsequently the Lewis acid, preferably as such or as aqueous solution, and the compound of the formula HI and/or IV - as such or dissolved in the non-polar solvent, preferably as such - to the compound of the formula Ha/El (most preferred: TMHQ or TMHQA(c)) and the solvent. The Bronsted acid is then continuously or batch-wise, preferably continuous!}', added to this mixture. Convenient1.}', the compound of the formula IL or 7>: i? added continuously to the corn-pound of the the formula na/II (most preferred: TMHQ or TMHQA(c)) within about 15 to about 1-80 minutes, preferably within about 30 to about 150 minutes, more preferably within about 45 to about 130 minutes. The Lewis acid is preferably added at once, i.e. in its full amount, to the mixture of the compound of the formula Ita/II (most preferred: TMHQ or TMHQA(c)) and the solvent. After completion of the addition of the compound of the formula HI or IV (in the non-polar solvent) the reaction mixture is suitably heated further at the reaction temperature for about 10 minutes to about 360 minutes, preferably for about 30 minutes to about 240 minutes. The working-up can be effected by procedures conventionally used in organic chemistry. STEP b OF PROCESS 2. STEP b of PROCESS 2a As will be readily apparent, the use of a compound of the formula n or Ha with Rl and R3, respectively, being hydrogen such as PTMHQ or an isomer thereof as a reactant in the process of this invention will result in the preparation of atocol or a tocopherol such as cc-tocopherol while, when using a compound of the formula H with R.1 being acetyl, propio-nyl, pivaloyl, H02C-CH2-CH2-CO, nicotinoyl or benzoyl and n being 3 the respective to-cyl alkanoate or tocopheryl alkanoate such as ct-tocopheryl alkanoate will be obtained. For the manufacture of a-tocopherol or a-tocopheryl alkanoate PTMHQ or PTMHQ A and optionallyone: ormoreisomersthereof, which are obtained asjninor.by-products. in -the-manufacture of PTMHQ or PTMHQA, prepared to any method known to the person skilled in the art can be used as starting material. This ring closure can be carried out using the same catalysts under substantially the same reaction conditions as described above for the reaction of compounds of the formula n (e.g. TMHQ: formula II with R1 = hydrogen; or TMHQA: formula n with R1 = acetyl, propionyl, pivaloyl, HOjC-C^-CHz-CO, nicotinoyl or benzoyl) or Ha with a compound of the formula ffi and/or a compound of the formula IV. Therefore, in cases, where e.g. PTMHQ or PTMHQA and optionally one or more isomers thereof are produced according to STEP a, i: is sufficient to simply prolong the reaction time of STEP a to realize STEP b, i.e. to prolong the reaction time for about 30 minutes to about 240 minutes, to increase the amount of catalyst and/or to increase the reaction temperature. PROCESSES 3 and 3a This reaction can be .carried out using the same catalysts under substantially the same reaction conditions as described above for step a) of PROCESS 2 and 2a. Depending on the land of catalyst, the amount of catalyst and the reaction temperature the reaction stops at the intermediates of the formula la/I or proceeds to the end products of the formula vn/vna. PROCESS 4 This reaction can be carried out using the same catalysts under substantially the same reaction conditions as described above for step a) of PROCESS 2 and 2a. The reaction proceeds to the final product of the formula X independent from the nature of the catalyst, the amount of catalyst and the reaction temperature. PROCESS 5A According to still another aspect of this invention, a compound of the formula VHc such as e.g. a-tocopherol or y-tocopherol, or any other tocol as described in DE-OS 21 60 103 on page 5 in the third and forth paragraph may be converted into its alkanoate (a compound of the formula VUIa), e.g. its acetate, by treatment with an acylating agent in the presence of a Lewis acid as the catalyst at reduced pressure, preferably at an absolute pressure of below 0.9 bar, or under pressure, jjreferably at an absolute jpressure.of, atjeajSt. .1^1.bar.,. More preferably the absolute reaction pressure varies from about 0.02 bar to about 0.9 bar (even more preferably from about 0.1 bar to about 0.9 bar, most preferably from about 0.2 bar to about 0.9 bar) and from about 1.1 bar to about 10.0 bar (even more preferably from about 1.1 bar to about 6.0 bar, even more, more preferably from about 1.1 bar to about 5.0 bar, most preferably from about 1.1 bar to about 3.0 bar). Therefore, the invention is also directed to a process for the manufacture of tocyl allca-noates in the presence of a Lewis acid as the catalyst a* reduced pressure, preferably at an absolute pressure of below 0.9 bar. or under pressure, preferably a: an absolute pressure of at least 1.3 bar, The acylation in accordance with that aspect of the invention can be carried out using acy-lating agents conventionally used in the acylation of tocopherols such as anhydrides or hal-ides. Examples of these are anhydrides or halides of alkanoic acids such as acetic acid, propi-onic acid, pivalic acid, succinic acid, nicotinic acid and benzoic acid. Preferably, acetic anhydride or acid chloride, especially acetic anhydride, are/is used. The molar ratio of the compound of the formula VTIc to the acylating agent in the reaction mixture conveniently varies from about 1 :1 to about 1:5, preferably from about 1 : 1 to about 1:3, more preferably from about 1:1.1 to about 1 : 2. Suitable Lewis acids are the ones named above. The amount of the Lewis acid used as the catalyst is based on the lesser molar amount of reactant, i.e. the compound of the formula VIIc or the acylating agent, and can be in the range of from about 0.006 mol% to about 2.0 mol%, preferably from about 0.0075 mol% to about 1.5 mol%, more preferably from about 0.01 mol% to about 1.0 mol%, hi the batchwise mode of operation. For continuous operation, the amount of catalyst will be adjusted to the size of the reactor and the flow of the reactants. It will be appreciated that the determination of the appropriate figures based on the figures for.batchwise operation is *witbin.no;rmal^kill^As in .the.ojther.processes of the invention the Lewis acid is added at once, i.e. in its full amount. Preferably the catalyst is added as an aqueous, solution or suspension. The temperature of the acylation is dependent on the catalyst system used and the temperature the reactants (resulting from former process steps) already have. The acylation reaction can be generally carried out at temperatures from about 20 to about 200°C, preferably from about 60 to about 1 SO°C, more preferably from about 80 to about 160°C. When in-dium(IH) salts are used as the catalysts, the acylation reaction is preferably carried out at temperatures below 120°C. more preferably from about 15 to about 1200C, most preferably at room temperature, i.e. from about 15 to about 40°C. The reaction can be carried out essentially in the absence of an additiona] organic solvent, which is preferred. "Essentially in the absence of an additional-organic solvent" in the context of the present invention means that essentially-no organic solvent is present during the reaction and that no organic solvent is deliberately added. It might, however, be possible that traces of organic solvent are present in the starting materials or the catalyst as impurities. In other words, the reaction is carried out in substance; i.e. no other compound except the compound of the formula VTIc, the acylating agent and the catalyst is intendedly used for the reaction, so that at the beginning of the reaction the amount of any substance except for the starting material, the compound of the formula VHc and the acylating agent, and except for the catalyst in the reaction mixture is Alternatively it is also possible to carry out the reaction in the presence of an additional organic solvent, e.g. pyridine. The reaction is conveniently carried out under an inert gas atmosphere, preferably gaseous nitrogen or argon. It is a particular feature of the acylation according to the present invention that when using chiral tocols and tocopherols, e.g. (enantiomeric pure) (R,R,R)-a-tocopheroL, the acylation proceeds substantially without epimerization in tire- presence tjfindijam(i]l) S2rts"as the catalysts and at a temperature below 120°C, e.g. from about 20°C to about 120°C. Thus, if e.g. CR,.R,J?)-a-tocopherol is used as starting material for PROCESS 5A, (R,R,R)-a-tocopheryl alkanoate is obtained. In especially preferred embodiments of PROCESS 5 A a-tocopherol (formula VTIb with n = 3; see above), (S-tocopherol (formula VTJ c with X1 = X3 = CH3, X2 = H and n = 3), y-tocopheroi (formula VTI c with X2 = X3 = CHs, X1 = H and n = 3) and 5-tocoph.erol (formula Vn c with X1 = X: = H, X3 = CHs and n = 3). preferably a-tocopherol and J3-tocopherol, more preferably a-tocophsrol, are/is acylated to the appropriate tocopheryl al-kanoates (compounds of the formula \TQ/VTJIa with s = 3 and R, X1, X" and X3 having the same meanings and preferences as above). More preferred the appropriate acetates are manufactured, especially with indium(III) salts (preferences see above) as the catalysts and at a temperature below 120°C, preferably at room temperature, i.e. a temperature between 15and40°C. PROCESS 5B It can be carried out using the same catalysts under substantially the same reaction conditions as described above for PROCESS 5A. Process for the manufacture of formulations of a-tocopherol or its alkanoates The a-tocopherol or its alkanoate obtained by one of the processes of the present invention can further be formulated by any method known to the person skilled in the art, e.g. as those disclosed in US 6,162,474, US 2001/0009679, US 6,180,130, US 6,426,078, US 6,030,645, US 6,150,086, US 6,146,825, US 6,001,554, US 5,938,990, US 6,530,684, US 6,536,940, US 2004/0053372, US 5,668,183, US 5,891,907, US 5,350,773, US 6,020,003, US 6,329,423, WO 96/32949, US 5,234,695, WO 00/27362, EP 0 664 116, US 2002/0127303, US 5,478,569, US 5,925,381, US 6,651,898, US 6,358,301, US 6,444,227, WO 96/01103 and WO 98/15195. The following Examples illustrate the invention further. Examples In the following examples minor amounts of the following by-products were obtained: PTMQ: phytyltrimethylquinone: (Figure Remove) PTD: phyiadienes = dehydrated by-products of IP (easily separable); BZF: bcnzofuranes: (Figure Remove) The analysis of the products was done by gas chromatography (GC) using an internal standard. Jeffsol EC50® is a solvent mixture available from Huntsman Corp., PO Box 15730 Austin, T-exasrUSA/Aatwerp-2Q3Q, Belgium, which -consists of .ethylene carbonate and pro-pylene carbonate in the volume ratio 1:1. If examples were carried out at "atmospheric pressure" (comparative examples), this indicates that the reaction was carried out at a pressure from about 0.96 bar to about 1.03 bar. Examples 1-32: Processes with InCk or In(OTfb as the catalyst Examples 1-14: Preparation of PTMHO Examples l-3jjnCla as the catalyst 12,88 mmoj of TMHQ and 8.58 mmol of IP were reacted in the solvent or solvent system given in Table 1 in the presence of InCla as the catalyst (amounts of the catalyst given in Table 1) and at atmospheric pressure. The reaction time was 2 hours. For further details arjd the results see Table 1. Examples 4 and 5: InCOTfh as the catalyst 12.88 mmol of TMHQ and 8.58 mmol of IP were reacted in a mixture of 20 nil of heptane and 20 ml of Jeffsol EC 50® in the presence of increasing amounts (see Table 1) of In(OTf>3 as the catalyst and at atmospheric pressure. For further details about the reaction conditions and the results see Table 1. Table 1: The amount of THMQ was 12.88 mmol in all cases, the amount of P was 8.58 mmol in all cases. (Table Remove) Examples 6 and 7: IrtCh as the catalyst Varying amounts of TMHQ were reacted with 17.17 mmol of IP in 45 nil of toluene at 110°C in the presence of 1.0 mol% of InCb - based on IP - as the catalyst and at atrnos-rhsric pressure. Further details and the results are presented in Table 2. Example .8: _In/OTfh a_s the catalyst TMHQ (38.63 mmol) and JP (25.15 mmol, 97%, added during 1 hour) were reacted in a molar ratio of 1.5: 1 in the presence of 1.0 mol% of In(OTi)3 as the catalyst (amount based on IP) at 22°C and at atmospheric pressure. For further details and the results see Table 2. After separation of the heptane phase and washing of the heptane phase with Jeffsol EC50® (60 ml) the resulting mixture (suspension in heptane) was filtered under vacuum. The pasty nearly colorless solid was analysed by GC. Example 9: InfOTfh as the catalyst TMHQ (24.691 g, 161.1 mmol) and "IP (38.833 ml, 107.4 mmol, 97%, added during 1 hour) were reacted in a molar ratio of 1.5 :1 in the presence of 1.0 mol% of In(OTfh as the catalyst (amount based on IP) at 22°C and at atmospheric pressure. For further details and the results see Table 2. After separation of the heptane phase and washing of the heptane phase with Jeffsol EC50® (250 ml) the resulting suspension in heptane was filtered under vacuum. The pasty nearly colorless solid was analysed by quantitative GC. Table 2: The amount of catalyst was 1.0 mol%- based on IP - in all cases. (Table Remove) Examples 10-14 200 mmol of TMHQ were reacted with 200 mmol of IP (examples 10 and .13) and 203 inmol of IP (examples 11, 12 and 14), respectively, in the presence of increasing amounts of In(OTf)3 (example 10) orlnds (examples 11-14) as the catalyst in 100 ml of an organic solvent. Examples 10 and 14 were carried out under pressure, whereby examples 11-13 were carried out at atmospheric pressure. For the reaction temperature, the pressure, the reaction time and the type of solvent see Table 3. Table 3: The amount of solvent was 100 ml in all cases. The amount of TMHQ was 200 mmol in all cases, hi the examples 11, 12 and 14 a molar excess of IP of 1.5 mol% based on the amount of TMHQ was used. The yield of PTMHQ is based on IP. (Table Remove) Examples 15-29: Preparation of (all-racVTCP jExamples 1S-16: Preparation of Call-mcVTCP at atmospheric, pressure In a 250ml Biichi reactor or an autoclave equipped with a stirrer, a thermometer, a pressure indicator, a Dean-Stark separator, and a reflux condenser 30.447 g (200 mmol) of TMHQ (99.97%), certain amounts of InCls (see Table 4; amounts based on IP) and 100 ml of toluene were heated at 114°C under a continuous nitrogen flow and under an absolute pressure of 1.0 bar. 74.035 ml (200 mmol) of IP (94.6%) were added at a feed rate of 1.234 ml per minute. Approximately 3.6 ml water were collected until the end of the reaction. After completion of the addition the reaction mixture was stirred for 1 hour at 114°C and cooled down to room temperature. The reaction mixture was concentrated under reduced pressure (45°C at 95 to 15 mbar). (all-rac)-TCP was obtained as a viscous oil. For the results see Table 4. Examples 17-18::Preparation of fall-racVTCP underpressure Examples 15 and 16 were repeated, but the reaction was carried out at 137°C under an absolute pressure of 2 bar. After 1 hour at 137°C the reaction mixture was cooled down to room temperature and once, at room temperature the pressure was released. For the results see Table 4, 5 (example 18 only) and 12 (example 18 only). Example 19: Preparation of Call-racVTCP underpressure In a 250ml Biichi reactor or an autoclave equipped with a srirrer, a thermometer, a pressure indicator, a Dean-Stark separator, and a reflux condenser, 30.447 g (200 mmol)'of TMHQ (99.97%,), 5 ml oflnClj (0.2 M aqueous solution, 0.5 mol%51 mmol) and 100 ml of heptane were heated at 147°C under a continuous nitrogen flow and under an absolute pressure of 3.4 bar. 75.304 ml (203 mmol) of IP (94.6%) were added at a feed rate of 0.605 ml per minute. Approximately 3.6 ml water were collected until the end of the reaction. After completion of the addition the reaction mixture was stirred for 1 hour at 147°C and cooled down to room temperature. Then the pressure was released. The reaction mixture was concentrated under reduced pressure (45°C at 110 to 15 mbar). (all-rac)-TCP was obtained as . a viscous oil (91.51 g). The yield was, 92.0% - based on IP. For the results see Table,4, 6, 7, 8 and 12. Table 4_: Comparison between experiments at atmospheric pressure and under pressure in toluene with InCla as the catalyst. The conversion of P was 100% in all cases. (Table Remove) Examples 20 and 22 (*): Preparation of (all-racVTCP with InCk as the catalyst in different solvents and under pressure 200 mmol of TMHQ and 203 romol of P (corresponding a molar excess of 1.38 mol% -based on the amount of TMHQ) were reacted in 100 ml of toluene at 137°C or in 100 ml of heptane at 147°C. The P was added during 120 minutes. Afterwards the mixture was reacted for further 60 minutes. All yields and selectivities (given in Table 5) are based on IP. See also Table 6. Examples 21, 23 and 24: Preparation of (all-7-acVTCP with different amounts of indium salts as the catalyst and underpressure 200 rnmol of TMHQ and 200 mmol of IP were reacted in 100 ml of toluene at 137°C or in 100 ml of heptane at 147°C. The P was added during 60 minutes. Afterwards the mixture was reacted for further 60 minutes. All yields and selectivities (given in Table 5) are based on IP. Table 5: Influence of the counterion of the indium salt. The amount of catalyst was 2.0 -mol%, basedon F5-iBvrf'Ca3e^Thet'Conversion"ofIP-was~100%"m all cases. * molar ex-" cess of IP of 1.38% (Table Remove) With InCb excellent yields were obtained in both solvents, heptane and toluene. The selectivity for the formation of the desired 6-membered ring product (all-nac)-TCP with this catalyst was very high compared to results with hi(OTfh as a difference of 28 to 30% for the selectivity was observed. It was also found that in heptane a small excess of P (+1.38 mol%) led to a much better yield (see Table 5, example 22) than carrying out the reaction with equimolar amounts of IP and TMHQ. In fact, (all-rac)-TCP could be isolated in 93.9% yield after work-up. It has to be emphasized that at atmospheric pressure a TMHQ/IP ratio of 1.5/1 had to be used whereas, under pressure, an .equimolar ratio was sufficient to produce the desired chroman ring compound (all-nzc)-TCP in excellent yield. It is noteworthy that the proportion of TMHQ used for these reactions under pressure was twenty-fold higher than at atmospheric pressure (4 mol/L instead of 0.2 mol/L)=and it did not affect the yield of the reaction. Example 25: Preparation of faU-racVTCP with InCk as the catalyst and under pressure 200 mmol of TMHQ and 203 mmol of IP were reacted in 100 ml of toluene at 137°C. The IP was added during 120 minutes. The reaction mixture was then further reacted for another 60 minutes. The yield - based on IP — is given in Table 6. See also Table 7. Example 26: Preparation of rall-rae)-TCP withjfoClg.as.thejaMyst.aDAjcider,pressure 200 mmol of TMHQ and 203 mmol of P were reacted in 100 ml of toluene at 137°C. The IP was added during 120 minutes. The reaction mixture was then reacted for further 566 minutes. The yield- based-on P - is given in Table 6. Example 27: Preparation of (all-racVTCP with InC% as the catalyst and underpressure 200 mmol of TMHQ and 203 mmol of P were reacted in 100 ml of heptane at 147°C. The P was added during 120 minutes. The reaction mixture was then further reacted for another 120 minutes. The yield - based on P - is given in Table 6. Table 6; Influence of the amount of InC^. The conversion of P was 100% in al. cases. (Table Remove) When the amount of InClj was reduced to 0.25 mol% (all-rac)-TCP was still obtained in good yield (see Table 6, examples 26 and 27). However a longer reaction time (e.g. up to 566 minutes in toluene, example 26) was needed to obtain nearly total ring closure. It appeared that best results were obtained (selectivity (yield)) for (all-nzc)-TCP using a catalyst amount of 0.5 mol% to 2 % InCls, especially in heptane. In toluene and in heptane, the desired chroman product (all-rac)-TCP could be isolated in 90.2 up to 96.0% yield. Example 28: Preparation of (all-racVTCP in cvclohexane at an absolute pressure of 4.0 i bar 200 mmol of TMHQ and 203 mmol of IP were reacted in 100 ml of cyclohexane at 135°C and under an absolute pressure of 4.0 bar in the presence of 0.5 mol% of InCls - based on IP. The IP was added during 120 minutes. Afterwards the mixture was reacted for further 380 minutes. The yield of (all-rac)-TCP given in Table 7 is based on IP. Example 29: Preparation of (all-mcVTCP in hexane underpressure 200 mmol of TMHQ and 203 mmol of IP were reacted in 100 ml of hexane in the presence of 0.5 mol°/o of InCl3 - based on IP. The IP was added during 120 minutes at 125°C and under an absolute pressure of 4.0 bar. Afterwards the mixture was reacted for further 180 minutes at 125°C and under an absolute pressure of 4.0 bar and further 206 minutes at " 13 5 °C and under an absolute pressure of 5.1 bar. The yield of (al]-rac)-TCP given in Table 7 is based on P. Table 7: Influence of the solvent. The conversion of IP was 100% in all cases. (Table Remove) One of the advantages of heptane compared to toluene was the absence of by-products such as phytyl-toluene compounds due to the solvent. Examples 19(-a>-19-e: Reproducibility All reactions were carried out in 100 ml of heptane with 200 mmol of TMHQ, 203 mmol of IP, 0.5 mol% oflnds under an absolute pressure of 3.4 bar and at 147°C. IP as added within 120 minutes. The reaction time was 60 minutes. All yields are based on IP. The results are summarized in Table 8. Table 8: Test of reproducibility, total conversion of IP: (Table Remove) An excellent reproducibility was found as only a 1.04% maximum variation of the yield was observed with an average yield cf 91.6% over five experiments. Examples 30-37: Processes with ScfQTfh as the catalyst Examples 30-31: Preparation of (all-rgc>-TCP with azeotropic removal of water In a Buchi reactor with a Dean-Stark separator 200 mmol of TMHQ and 200 mmol of P were reacted in 100 ml of toluene in the presence of 0.1 mol% of Sc(OTf}3 -based on IP. The P was added during 60 minutes at the temperature and at the pressure given in Table 9. Afterwards the mixture was reacted for further 60 minutes at the same temperature and pressure. The yield and selectivity of (all-rac)-TCP given in Table 9 is based on IP. Example 32: Preparation of Call-racVTCP without azeotropic removal of water In an autoclave reactor 200 mmol of TMHQ and 200 mmol of P were reacted in 100 ml of toluene in the presence of 0.1 moP/o of Sc(OTf}3 - based on P. The IP was added during 60 minutes at an absolute pressure of 3.6 bar and at a temperature of 140°C. Afterwards the mixture was reacted for further 60 minutes at the same temperature and pressure. The yield and selectivity of (all-rac)-TCP given in Table 9 is based on IP. Example 33: Preparation of (all-racVTCP_without azeotropic removal of water In a 250 ml autoclave reactor equipped with a mechanical stirrer, a thermometer and a pressure indicator 34596 g (221 mmol) of TMHQ (98%), 1 mmol of Sc(OTf)3 (0~.5 mol% - based on P) and 50 ml of toluene were heated at 140°C under nitrogen atmosphere and under an absolute pressure of 5.6 bar. 72.350 ml (200 mmol),of IP .(97°/0) were added at a feed rate of 2.412 ml per minute. After completion of the addition the reaction mixture was stirred for one hour at 140°C, cooled down to room temperature and when room temperature was reached the pressure was released. The reaction mixture was concentrated under reduced pressure (45°C at 95 to 15 mbar). A viscous oil (94.76 g) was obtained and analysed by quantitative GC. The yield of (all-rac)-TCP was 81.4% - based on IP. gxamples 34 and 35: Preparation^ of (all-7-acVTCP_with azeotropic removal of water Examples 30 and 31 were repeated, but instead of 0.1 mol% of Sc(OTf)3 1.0 mol% of Sc(OTf)3 were used. The yield and selectivity of (all-na^-TCP, based on P, is given in Table 9. Example 36 Example 35 was repeated but the reaction was carried out-at a higher temperature and at a higher pressure, For details and the results see Table 9 and 12. ffxanrole 37: Preparation of (all-racVTCP without azeotropic removal of water Example 32 was repeated, but instead of 0.1 mol°/o.of Sc(OTfb1.0 mol% of Sc(OTfb were used. The yield and selectivity of (all-rac)-TCP, based on IP, is given in Table 9. Table 9: Comparison between experiments at atmospheric pressure and under pressure in toluene with Sc(OTfb as the catalyst. (Table Remove) Examples 38-47: Processes with Fe/HClas the catalyst Example 38: Preparation of fall-7-qcVTCP in a Biichi reactor In a 500 ml Biichi reactor equipped with a stirrer, a thermometer. 2 pressure indicator, a Dean-Stark separator and a reflux condenser 91.3 g (595 mmol) of TMHQ (99.5%): 0.16 g (2.S6 mmol} of iron powder and 137 g of toluene were heated to ]4D°C under a continuous argon flow and under an absolute pressure of 1.9 bar. When the temperature of the reaction mixture was 140&C hydrogen chloride was added to the reaction mixture at a feed rate of 0.333 g per minute for the next 5 hours (30 minutes of saturation, 4 hours addition of IP and 30 minutes further reaction afterwards; altogether 100 giof gaseous HC1 were used during these 5 hours). After 30 minutes under hydrogen chloride flow at 136°C and under an absolute pressure of 2.05 har, 187.9 g (616 mmol) of IP (97.5%) were added at a feed rate of 0.78 g per minute. During the addition of IP (4 hours) the temperature of the reaction mixture increased from 136°C to 146°C. Approximately 14 ml of aqueous phase were collected until the end of the reaction. After the addition of IP was completed the reaction mixture was stirred for further 30 minutes at 146°C, then the hydrogen chloride flow was stopped, replaced by an argon flow and the solution was cooled down to room temperature. When room temperature was reached the pressure was released. The reaction mixture was concentrated under reduced pressure (45°C at 95 to 15 mbar). A viscous oil (270.2 g) was obtained and analysed by quantitative GC. The yield of (all-7-ac)-TCP was 91.5% - based on P. Examples 39-42: Preparation of (all-/-ac>-TCP underpressure Example 38 was repeated with the same amounts of TMHQ, IP and Fe. The amount of HC1 and the time for the addition of IP were, however, different. The pressure, under which the reaction was carried out was also slightly different in the examples 39-41. For further details and the results see Table 10 and 13 (examples 41 and 42 only). Examples 43-46: Preparation of Call-mcVTCP at atmospheric pressure " In a Btichi reactor with,a-D-ean-Statk. separator. 600 mmol of.TMHQ and varying amounts of IP (see Table 10) were reacted in 137 g of toluene (only example 48 and 49:171.1 g toluene) in the presence of varying amounts of iron powder and fed gaseous HC1 (see Table 10). The gaseous HC1 was added with a feed rate of 0.333 g per minute to the TMHQ in toluene. The mixture of TMHQ and toluene was saturated with HC1 during 30 minutes before the IP was added during the time given in Table 10 and at an absolute pressure of 1.0 bar under a continuous HC1 flow. After the complete addition of IP the mixture was . reacted for further 30 minutes at the same temperature and pressure and the continuous HC1 flow. Then the HC1 flow was stopped and the reaction mixture worked-up. The yield and selectivity of (all-rac)-TCP given in Table 10 is based on IP. Example 47: Preparation of (all-racVTCP underpressure Example 46 was repeated but the reaction was carried out under an absolute pressure of 2.1 bar instead of 1.0 bar. Further details and the results are shown in Table 10. Table 10: Comparison between experiments at atmospheric pressure (examples 43 - 46) and under pressure (examples 38-42 and 47) in toluene (under reflux) with Fe/HCl as the catalyst; the conversion of IP was 100% in all cases. All yields and selectivities are based on IP. (Table Remove) Examples 48-53: Processes with ZnCli/HCl as the catalyst Example 48: Preparation of (all-rac)-TCP in heptane in the absence of an amine at atmospheric pressure 322,rnmol of TMHQ and 320 mmol of IP were reacted.in 163.3g of heptane, under reflux in the presence pf ZnCb and gaseous HC1 as the catalyst (amounts see Table 11). The reaction was carried out at 1.0 bar. Further details and the results are given in Table 11. Example 49: Preparation of (all-raeVTCP in heptane in the absence of an amine under pressure Example 48 was repeated, but the reaction carried out under an. absolute pressure of 2.1 bar and not at 1.0 bar. Further details and the results are given in Table 11. Example 50: Preparation of (all-nacVTCP in hexane in the presence of an amine under pressure In a 500 ml Buchi reactor equipped with a stirrer, a thermometer, a pressure indicator, a Dean-Stark separator and a reflux condenser 60 g (394 mmol) of TMHQ (99.5%), 12.5 g (91.7 mmol) of ZnCl2j 1.2 g of tridecylamine and 177.7 g of hexane were heated to 92°C under a continuous argon flow and under an absolute pressure of 2.2 bar. When the temperature of the reaction mixture had reached 92°C gaseous hydrogen chloride was added to the reaction mixture at a feed rate of 0.035 g per minute to saturate the reaction mixture with HC1. (The HC1 flow was continued during the addition of IP and the further reaction time, i.e. gaseous HC1 was added during 2.5 hours.) After 30 minutes under hydrogen chloride flow at 94°C and at an absolute pressure of 2.2 bar, 122.6 g (403 mmol) of IP (97.5%) were added at a feed rate of 2.05 g per minute. During the addition of IP the temperature of the reaction mixture''increased from 94°C to' 100°G. Approximately 7.4 ml of an aqueous phase were collected until the end of the reaction. After all IP was added the reaction mixture was stirred for further 60 minutes at 102°C, then the hydrogen chloride flow was stopped (A total of 5.3 g of hydrogen chloride were used during the 2.5 hours.), replaced by an argon flow and the solution was cooled down to room temperature. When room temperature was reached, the pressure was released. The reaction mixture was concentrated under reduced pressure (45°C at 110 to 15 rnbar). A viscous oil (176.88 g) was obtained and analysed by quantitative GC. The yield of (all-rac)-TCP was 94.9% -based on IP. Example 51: Preparation of (all-racVTCP in hexane in the presence of an amine under pressure Example 50 was repeated, but instead, of 403 mmol of IP 404 mmol of IP were added and instead of 5:3 g of gaseous HC1 49.9 g of gaseous HCI were used. For further details:and the results see Table 11. Example 52: Preparation of jfaH-raeVTCP in hexane in the presence of an amine at atmospheric pressure Example 51 was repeated with the amounts of TMHQ, IP, ZnCli, tridecyl amine and gaseous HCI given in Table 11. The reaction, however, was not carried out at 2.2 bar, but at 1.0 bar. The results are presented in Table' 11. Ejxample 53: Preparation of (all-mcVTCP in heptane in the presence of an amine at atmospheric pressure Example 51 was repeated with the amounts of TMHQ, IP, ZnCk, tridecyl amine and gaseous HCI given in Table 11. The reaction, however, was not carried out in itexane, but in heptane. The results are presented in Table 11 and 13. Table 11: Comparison between experiments at atmospheric pressure (1.0 bar) and under pressure (2,1- 2.2 bar) in heptane under reflux (examples 48, 49 and 53) or hexane under reflux (examples 50-52) with ZnCl2/HCl(g) as the catalyst. IP was added during one hour in all cases. All yields and selectivities are based on IP. The conversion of IP was 1.00% in all cases. (Table Remove) Example 54: Preparation of Call-7-acV3.4-dehvdro-oc-tocopherol 15.22 g (99.2 mmol) of TMHQ (99.2%), 29 mg (0.5 rnmol) of iron powder and 70 ml of toluene were added to a 200 m] flask equipped like the Biichi reactor and the resulting beige suspension was stirred at 750 rounds per minute. The reaction mixture was heated to I11 °C at a constant heating rate of 2 K per minute. HC1 was added at a -flow rate of 33.8 ml per minute and argon was added at a flow rate of 3.5 ml per minute. After 45 minutes the reaction temperature of 111°C had been reached and 31.01 g (102,4 mmol) of 1,2-dehydroisophytoi (97.3%; from Teranol in Lalden, Switzerland) were added at a feed rate of 0.13S g per minute during 225 minutes. During the addition of the 1,2-dehydroisophytol toluene was slowly distilled off in order to'keep the volume of the solution constant during all the reaction. The reaction temperature also increased from 111 °C to 15T*C. After completion of the addition of 1,2-dehydro-isophytol the reaction mixture was stirred at this temperature for 45 minutes and cooled down to room temperature. When the heating was switched off, the HC1 flow was stopped and replaced by a stronger argon flow. After 1 hour the temperature of the reaction mixture was 60°C. The reaction mixture was then concentrated under reduced pressure (60°C at 300 to 18 mbar). The resulting oil was further concentrated under reduced pressure (60°C at 0.3 to 0.1 mbar) during more than 2 hours to yield the crude product (45.6 g). A qualitative GC analysis of the crude product showed that it contained mainly TMHQ (25.6%) and (all-r0c)-3,4-dehydro-a-tocopherol (21.1%). The crude product was purified by two successive column chromatographies (first with ethyl acetate/hexane - 1/9 (v/v; silica gel 60 (Merck), particle size 0.063 - 0.2 mm) and finally with ethyl acetate/hexane = 1/19 (v/v)) to yield (all-r 1. A process for the alkenylation of phenols comprising 0 to 4 methyl groups, a total of 1 to 3 hydroxy groups and at least one unsubstituted position, whereby the unsubstituted position is ortho to a hydroxy group, with a compound of the formula HI and/or IV (Figure Remove) with R2 being hydroxy, acetyloxy, benzoyloxy or halogen, n being an integer from 0 to 3, and whereby the reaction is carried out in an organic solvent in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst at an absolute pressure of at least 1.1 bar, preferably at an absolute pressure of from 1.1 bar to 20.0 bar. 2. The process as claimed in claim 1, wherein the phenol has the formula Ha (Figure Remove) with X1, X2 and X3 being independently from each other hydrogen or methyl and R3 being hydrogen, acetyi, propionyl, pivaloyl, HO2C-CH2-CH2-CO, nicotinoyl or benzoyl, with the proviso that R3 is only acetyi, propionyl, pivaloyl, CHr-CO, nicotinoyl or benzoyl, if X1, X2 and X3 are all methyl. 3. The process as claimed in claim 1, wherein the phenol has the formula n (Figure Remove) with R1 being hydrogen, acetyl, propionyl, pivaloyl, HOsC-CHr-CHr-CO, nicotinoyl or benzoyl. 4. ~K process for the manufacture of compounds of the formula Vila by a) (STEP a) optionally reacting a compound of the fonnula Ila with a compound of the formula in and/or IV in an organic solvent (Figure Remove) b) (STEP b) submitting in an organic solvent a compound of the formula la and optionally one or more double bond isomers thereof, all obtainable by step a), to ring closure to form chroman derivatives Vila, with R2 being hydroxy, acetyloxy, benzoyloxy or halogen, R3 being hydrogen, acetyl, propionyl, pivaloyl, HO2C-CH2-CH2-CO, nicotinoyl or ben- zoyl, X1, X2 and X3 being independently from each other hydrogen or methyl, with the proviso that R3 is only acetyl, propionyl, pivaloyl, H02C-CH2-CH2-CO, nicotinoyl or benzoyl, if X], X2 and X3 are all methyl, and n being an integer from 0 to 3, whereby at least one of the steps a) and b) is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst at an absolute pressure of at least 1.1 bar, preferably at an absolute pressure of from 1.1 bar to 20.0 bar. 5. A process for the manufacture of chroman derivatives Vila (Figure Remove) by reacting of phenols comprising 0 to 4 methyl groups, a total of 1 to 3 hydroxy groups and at least one unsubstituted position, whereby the unsubstituted position is ortho to a hydroxxgroiip, with a compound of the formula HI and/or IV (Figure Remove) with R2 being hydroxy, acetyloxy, benzoyloxy or halogen, and n being an integer from 0 to 3, whereby the reaction is carried out in an organic solvent in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst at an absolute pressure of at least 1.1 bar, preferably at an absolute pressure of from 1.1 bar to 20.0 bar. 6. The process as claimed in any of the preceding claims, wherein n in the formula HI 15 and IV is 3. 7. A process for the manufacture of alkanoates of the formula VHIa, (Figure Remove) wherein n is an integer from 0 to 3, X1, X2 and X3 are independently from each other hydrogen or methyl, and R is selected from the group consisting of acetyl, propionyi, pivaloyl, HOaC-CHj-CH^-CO, nicotinoyl, and benzoyl, - characterized in that the reaction is carried out in the presence of a Lewis acid as the catalyst at an absolute pressure ofbelow 0.9 bar or at an absolute pressure of at least 1.1 bar, preferably at an absolute pressure of from 0.02 to 0.9 bar or from L.I bar to 10.0 bar. B. The process as claimed in claim 7, wherein X1, X2 and X3 are methyl and n = 3. 9. The process as claimed in any of the preceding claims characterized in that the Lewis acid used as the catalyst is indium trichloride, indium tribromide, indium triiodide, indium triacetate, indium tris[bis(trifluoromethanesulfonamide)], indium triflate or scandium triflate. ID. The process as claimed in any of the preceding claims characterized hi that the mixture of a Lewis acid and. a Bronsted acid used as the catalyst is a mixture nfZnCb with HC1 or Fe and/or FeCl2 with HC1. 31. The process as claimed in claim 8 characterized in that the cx-tocopherol used (formula VIIc with X1 = X2 = X3 = methyl and n = 3) is the reaction mixture obtained by step b) of the process according to claim 4. " 12. The process according to claim 4 characterized in that all steps are carried out at an absolute pressure of at least 1.1 bar, preferably at an absolute pressure of from 1.1 bar to 20.0 bar. 13. The process according to one or more of claims 1 to 6 and according to one or more of claims 9 to 12 as far as they refer to one or more of the claims 1 to 6, characterized in that the organic solvent is a non-polar aprotic organic solvent. 14, The prdcess'accbrding to claim 13 characterized in that the non-polar aprotic organic solvent is selected from the group consisting of cyclohexane, hexane, heptane, octane, 1,1,1-trichloroethane, 1,2-dichloroethane, methylene chloride, methylene bromide, benzene, toluene, o-xylene, m-xylene, p-xylenej chlprobenzene, l,2=dichlorobenzene, 1,3-dichlorobenzene and 1,4-dichlorobenzene. 15. A process for the manufacture of alkanoates of a-tocopherol, p-tocopberol, y- tocopherol and 6-tocopherol, preferably of alkanoates of a-tocopherol, more prefera bly of a-tocopherol acetate, wherein an a-tocopherol, (3-tocopherol, y-tocopherol and 8-tocopherol, respectively, obtained by a process according to any one of the preced ing claims is reacted with an acylating agent. 16. A process for the manufacture of alkanoates of a-tocopherol, ^-tocopherol, y- tocopherol and 6-tocopherol by reacting .a-tocopherol, p-tocopherol, y-tocopherol and 6-tocopherol, respectively, with an acylating agent selected from the group consisting of the anhydrides and halides of acetic acid, propionic acid, pivalic acid, succinic acid, nicotinic acid, and benzoic acid, characterized in that the reaction is carried out in the presence of an indium(III) salt as the catalyst, preferably at temperatures below 120°C. 17. A process for the manufacture of formulations of a-tocopherol, P-tocopherol, y-tocopherol, 5-tocopherol or their alkanoates, preferably of a-tocopherol or its alkanoates, whereby cc-tocopherol, p-tocopherol, y-tocopherol, 5-tocopherol or their alka- noates, respectively, preferably a-tocopherol or its alkanoates, obtained by a process according to one or more of the preceding claims are used. by reacting a compound of the formula II with a compound of the formula DC 18. A process for the manufacture of a compound of the formula X (Figure Remove) in an organic solvent with R1 being hydrogen, acetyl, propionyl, pivaloyl, HOsC-CHa-CH^-CO, nicoti- noyl or benzoyl R2 being hydroxy, aceryioxy, benzoyloxy or halogen, and n being an integer from 0 to 3, whereby the reaction is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst at an absolute pressure of at least 1.1 bar, preferably at an absolute pressure of fro 1.1 bar to 20.0 bar. 19. A process for the manufacture of corapcmnds of the fwsnula X with R.' being acetyl, propionyl, pivaloyl, HOjC-CHr-CHs-CO, nicotinoyl or benzoyl, (Figure Remove) (X) by reacting a compound of the formula X with R1 being hydrogen with an appropriate acylating agent, wherein n is an integer from 0 to 3, characterized in that the reaction is carried out in the presence of a Lewis acid as the catalyst at an absolute pressure of below 0.9 bar or of at least 1.1 bar, preferably at an absolute pressure of from 0.02 to 0.9 bar or from 1.1 bar to 10.0 bar.

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