the" Rev. 1981. 81,415430 415

The Michaelis-Arbuzov Rearrangement

ALOK K. BHATACHARYA' RegkMa/ Research lnlmratcfj? Jomat 785008, Mia

0. THYAGARMAN RegkMal Researm Lalmrahny, -bad 5woo9. I&

ReceM August 3. 1978 (ReWMsnwt Recehgd Jammy 1. 1981)

Contents 1. Introduction 415 11. Reaction Mechankm 416 111. Scope and Limitation of the Reaction 417 A. Alkyl MMes 410 B. Tricoordinate phosphorus Reactant 420 C. Effectivenessof Catalysts 42 t IV. Synthetic Applications 42 1 A. Synthesis of 421 B. Synthesis of 422 C. Synthesis of Tertiary Filosphine Oxldes 423 0. Synthesis of Phosphonyl and Phosphinyl 424 AM Bhattachafya was born h Dacca, (undivided) India. in 1942. Haldes He took his Ph.D. in SyntheHC organic chemistry in 1967 from E. Other SyntheHc Applications 424 Banaras Hindu University. He went to Canada for fdmr studles of and from 1968 to 1970 worked in Ih-3 University of Regina and V. Behavwur Sulfur and Fluorine Analogues 425 McGiil University. Monbeai. After a few years of teaching gadw under Arbuzov Condnions ales and undergraduates. he joined Ih-3 Regional Research Lab A. Trialkyi Trithiiphosphtes 425 ratory. JOmat. India. as a scientist and worked there on wgano- B. Alkyl Phosphonodithioites 425 phosphorus compounds and indusMal chemicals. He is presenlty wah Hindustan Insecticides Limited, New Deihi. doing pesticide C. Phosphinodiiones 425 research. 0. Organofiuorine Compounds 425 VI. Rearrangement of Phosphnes in the Presence 426 of Compounds Not Containing Halogens VII. References 427 I. Introductbn The Michaelis-Arbuzov rearrangement, also known as the Arbuzov rearrangement, Arbuzov reaction, or Arbuzov transformation, is one of the most versatile pathways for the formation of carbon-phosphorus bonds and involves the reaction of an of trivalent phosphorus with alkyl halides. The reaction, originally discovered by Michaelis' in 1898, was explored in great Gopahkrkhna Thyagarajan is dlrector of the Regional Research detail by Arbuzov2 and several subsequent investigators. Laboratory in Hyderabad. Andhra Pradesh. India. Bom in 1934, he received his Ph.D from Osmanla University. Hyderabed (1963). The rearrangement is one of the most thoroughly in- and dM postdoctorai work with Rofessor Henry Rapoport at the vestigated among organophosphorus reactions and is University of California. Berkeley (1964-1965). He was Visning widely employed for the synthesis of phosphonates, Scientist (1969-1971) at Uw Nafbnai Insmutes of Health. Beme&. phosphinic acid , and oxides. MD. in the laboratory of h. Everette L. May. NIAMD. His interests In its simplest form the Arbuzov arrangement is the in organic chemistry relate to heterocyclic synthesis. chemical examination of Indian flora. and development of manufacturing reaction of an alkyl halide with a trialkyl phosphite, knowhow for pesticides. drugs. and industrial organic chemicals. yielding a dialkyl alkylphosphonate (1). Thus, during He wedearlier (1975-1980) as dieclor of the Regional Research 0 Laboratory. Joht. Assam A ll/OR IROlsP + R'-hal - R-P + R-ha1 the transformation a tervalent phosphorus (Pm)is 'OR converted into a pentavalent phosphorus (Pv). In 1 general, the alkyl group of the halide gets attached to R= alkyl, aryl, etc. the phosphorus, and one alkyl from phosphorus com- R' = alkyl, acyl, etc. bines with halogen to form the new alkyl halide. ha1 = CI, Br, I The rearrangement has been discussed in a book on organophosphorus compounds3 and in two review& Adhcorm ndena to Hindustan Insecticides Limited, Guru dating hack to 1964. To date there is no available re- Gobind Singh #q,New Delhi 110015, India. view of the subject in English, though several have

0009-2665/8110781-0415$06.0010 0 1981 An-" chsmlcal society 416 Chemical Reviews, 1981, Vol. 81, No. 4 Bhattacharya and Thyagarajan

Et Et appeared in German5v6and Ru~sian.~The present ef- E+\+/MeP \;/ fort, which covers the literature through December 1978, is aimed at providing more recent information on Et/I-'OEt Et/I-\OEt the topic. The subject matter includes the mechanism, 5 6 scope of the reaction, synthesis of different kinds of 18-21 "C for 15-25 days resulted in their decomposition organophosphorus compounds via rearrangement, re- to the phosphine oxides. cent modifications, i.e., the rearrangement of trialkyl In the case of alkyl esters, the phosphonium inter- phosphites in presence of nonhalogen compounds, be- mediate 2 cannot normally be isolated. However, by havior of sulfur and fluorine analogues under Arbuzov employing a methylating agent with a very weakly nu- conditions, and also some discussion about anomalous cleophilic leaving group, e.g., methyl trifluoro- Arbuzov reaction. methanesulfonate, the phosphonium salts with trialkyl phosphites also have been is01ated.l~ A stable 1:l in- II. Reaction Mechanism termediate, however, can be obtained in several in- On the basis of numerous investigations&'l the fol- stances from triaryl phosphites1620and in other special lowing mechanism may be written for the rearrange- cases involving triaryl phosphites and a,&dihaloalkyl ment. ethers. In the reaction of carbonium salts such as tri- phenylmethyl tetrafluoroborate the intermediate could also be obtained.21*22Tris(neopenty1oxy) phosphite on mixing with methyl iodide in equimolar proportion at room temperature is also reporteda to give a crystalline 2 Michaelis-Arbuzov intermediate, 7, which decomposed The lone pair of electrons of the phosphite attacks the 0 alkyl group of the alkyl halide to form the addition + - CHCI3 II compound 2 in which the alkyl group of the alkyl halide ( Me3C- CH20)3PMe I -(Me3C)-cH2y( Me3C-CH20)3P-Me gets attached to the phosphorus. In the next step an 7 8 alkyl group of the phosphite dissociates from 2, re- in chloroform in a first-order reaction to give the sulting in the formation of the P=O bond; the alkyl phosphonic acid diester 8. group is eliminated as the new alkyl halide. The overall Alkali alcoholates or sodium bicarbonate also causes result of the two steps is the conversion of trivalent cleavage of 7 to 8. In general the intermediates from phosphorus into pentavalent. When the alkyl groups triaryl phosphites and alkyl halides could be cleaved of the phosphite and the alkyl halides are identical, i.e., thermally (above 200 "C) or by reaction with R = R', the process amounts to an isomerization of the or bases to give the phosph~nates.'~ phosphite. In his classic Arbuzov formulated the penta- It is reported that the conversion of >P-0-C coordinated compound as the intermediate in the re- linkage into >P(=O)--C involves a net gain of 32-, and arrangement and gave structure 9 to the addition com- possibly 65,kcal/mol energy in the total bond stabil- ity12 and acts as a driving force for the rearrangement. OR However, an accessible path for the redistribution of I ,OR '-BueP(oMe) p-/o-cHZ O-CHrC- \ Me RO- T\ I u electron density is also required to effect the conversion. (CIS and \ / Haloalkyl phosphites undergo internal rearrangement X trans) 0-CH2 on heating the halogen present in the phosphite itself 9 10 11 acting as an alkyl halide. For example, tris(&chloro- pound of phosphite and alkyl halide. Although a num- ethyl) phosphite (3)l3 undergoes isomerization to the ber of these addition products, in crystalline state, have 4 on heating to about 150 "C. been known for a long time, not much had been said CQ by the earlier worker^^.^,^ about their structure except CICHzCH 0 referring to them as "quasiphosphonium salts". The * \p:/-CH2 I-- P-X bond in these compounds has been reportedl6P2O CICH2CH20 ' '0-CHz to be partially ionic and partially covalent in nature. 3 A phosphonium salt structure (2) is also very widely used for these products. rearrangement The mechanism of the reaction has been studied with - a number of five- and six-membered-ring phosphites. These compounds exist in a mixture of cis and trans U forms. It was observed that the five-membered cyclic CICHzCHzO 11 phosphites could be oxidized stereospecifically by ni- 'P-C H2CH2C I CICH2CHzO/ trogen tetroxide to the .26 Similarly high stereoselectivity was also noted in reaction of six-mem- 4 bered-ring systems with halides2' and free radicals.27c The Michaelis-Arbuzov reaction of esters Thus a mixture of trans and cis phosphites 10 on re- also proceeds by way of quasiphosphonium interme- action with CHJ gave the methyl phosphonates in diates of the above type. Evidence for their formation practically the same proportion^.^^" Similarly, ethyla- is obtained by the isolation14of crystalline 5, mp 56-58 tion of ethyl phenyl via ethyl (trimethyl- "C. A similar compound, 6, mp 79-81 "C, was also sily1)phenyl and some allied systems also obtained from the reaction of the phosphorus ester with proceeds with almost complete retention of configura- ethyl iodide. Storage of these products over P205at tion. Michaelis-Arbuzov Rearrangement Chemical Reviews, 1981, Vol. 81, No. 4 417 The stereochemistry of the reaction has been used by kylation step show evidence for an equilibrium between different workersmto distinguish between two possible phosphorane and phosphonium species.37 pathways. Thus Wadsworth and co-workersBatreated Decomposition of alkoxyphosphonium intermediates the six-membered cyclic phosphite system with various 2 resulted from the nucleophilic attack of X- on R to nucleophiles and observed that the outcome of the re- form phos horyl groups that provide the driving force action was influenced by the basicity of the attacking for the P' I!)to Pv transformations. The importance of nucleophile. In the above reaction the added cations nucleophilicity of the negative ion in effecting the de- also influenced the stereochemistry in a dramatic composition is further exemplified by the stability of manner.29b Using the stereochemistry some workers alkoxyphosphonium hexachlor~antimonates,~~ni- have proposed that the first step in the reaction is the trate~,~~and tetrafluorob~rates;~~ the anions of these formation of an alkoxyphosphonium salt followed by salts are essentially nucleophilic. dealkylation to the corresponding phosphoryl com- The general mode of attack of R by X- follows an sN2 pound. Hudson and Brownw attempted to explain the mechanism, X- attacking from the back side with si- stereochemistry of the phosphorus heterocycles in the multaneous 0-R bond-breaking and R-X bond for- terms of the effect of ring strain. mation. This is supported by the observationMthat in The studies on the reaction of diasteroisomeric cyclic the decomposition of the alkoxyphosphonium salts 16, phosphites with alkyl halides revealed a lack of ste- which are analogous to 15, inversion of configuration reospecificity at phosphorus which was explained by the of the asymmetric carbon in 17 did occur. intermediacy of a pentacovalent intermediate.30i31 H Bodkin and Simpson have suggested30 that in the "normal" Arbuzov reaction with alkyl halides, the pentacoordinate species 12 is formed initially and sub- sequently either dissociates into the phosphonium salt 13 or is dealkylated. 16 H 0 /R" i PCI I* Et1 decomposition Me-C*-OH 3 (Me-C-013P - 16 C>P-OFf' 4- R"I - CokrI I I OR' CIH13 (+) 12 H O H I* il I* J t (Me-C -0)zP-Et + Me-C-I I I c6H13 C6H13 (-) 17 13 In conformity with the sN2 mechanism, the reactiv- ities of mixed trialkyl phosphites are known16 to de- A 31P NMR study of these compounds could give crease with R in the order Me Et i-Pr. However, more insight into their structure as P(V) and P(IV)+ > > a carbonium ion mechanism can also operate during the are to absorb at different fields. In recent decomposition step of the intermediate:=t4l R first gets st~dies~~?~~on sterically hindered phosphites, the in- dissociated from the phosphonium salt and is then at- termediates have been actually isolated and charac- tacked by the X-. Support for this mechanism is pro- terized by 31P NMR, which suggests a phosphonium vided by the phosphinite esters bearing tertiary alkyl structure for these intermediates. A phosphonium in- substituents which also undergo the rearrangement41p42 termediate was also detected%in the bromination of 11. (eq 1). Thus both sN2 and sN1mechanism are possible. However, the authorsN were of the view that the pen- tacovalent species could have been formed as a short- Me Me Me Me lived intermediate en route to the phosphonium Me1 \+ ionization 'P-0-C-Bu I Me-P-0-C-Bu I structure. / - Et I Et/I- I More recently direct evidence by 31P NMR spec- the the trometry has been adduced36 for the formation of a Me Me five-coordinate intermediate in the reaction of 14 with \ Me--\C+I- + Me-P=O (1) BU/ Et/

III, Scope and Limitation of the Reaction 14 The two reactants in the Arbuzov rearrangement are alkyl halide and trialkyl phosphite. In a general way the reaction may be written a,X=Y=Cl b,X=Y=Br c, X= C1; Y = Ph elemental chlorine, bromine, and benzenesulfenyl 18 chloride. Studies on the stereochemistry of the deal- where A and B may be same or different alkoxy groups. 418 Chemical Reviews, 1981, Vol. 81, No. 4 Bhattacharya and Thyagarajan This enables a wide choice of phosphites as well as alkyl Haloalkyl amide59and N,N-bis(haloalky1)acrylamide halides to bring about the formation of a carbon- (21Palso react according to eq 2; a-allyl halides (22) phosphorus bond and makes the Arbuzov rearrange- ment a versatile synthetic tool. In some cases catalysts are useful, even necessary. Thus, the scope of the re- action is limited only by the availability of phosphites and alkyl halides and in applicable cases on the effec- Eke tiveness of the catalysts used. 21 A. Alkyl Halides It appears that any halide capable of reacting with nucleophilic reagents by an sN2 mechanism and not containing any potentially interfering groups (such as carbonyl or nitro) is suitable for the reaction. Generally the reactivity of organic halides follows the sequence43 RCO-ha1 > RCHz-hal > RzCH-ha1>> RR’R”C-hal; RI Cl > RBr > RCI. 22 Whereas the primary alkyl halides react normally, tertiary alkyl halides and simple aryl and vinyl halides react with phosphites as expectedfl and internal allyl are unreactive toward trialkyl phosphites, in conformity halides may partially undergo allyl shifts. with their behavior toward sN2 reactions. Benzyl, di- Similarly, with 23 and 24 the expected phosphonates phenylmethyl, and triphenylmethyl halides all give are obtained.62

n n expected phosphonates,u4 as do halogenomethyl de- U U rivatives of condensed aromatic hydrocarbon^;^^ e.g., LOR with benzyl bromide44b CI-CH=CH-CI -P(ORl3 Ro\II ,P-CH- -CH-P 23 RO \OR h 0 CHZBr P(OR3 I I ,OR MeCH=CHBr - MeCH=CH - P 24 \OR R= Et Propargyl halides (25) reactm as in eq 3. 27 is further R = Et, Me,CH, Pr, ClCH,CH, The aliphatic halides used have mostly been primary halides. Only a few secondary halides react satisfac- torily, e.g., isopropyl iodide48 and ethyl a-bromo- propionate.49 Generally the secondary and tertiary alkyl 25 \ 26 (3) halides either fail to react or may decompose to give olefins. In addition to alkyl halides other organic halides also react with trialkyl phosphites according to the Mi- 28 27 chaelis-Arbuzov scheme. Thus esters of 2-bromo- isomerized to 28 in the presence of bases. ethanol with aliphatic carboxylic acids,%halogen ethers, Acyl chlorides react readily to form a-ketophosphonic and acyl halides51react normally. Esters of a-monohalo acid esters. Maleic acid dichloride yields only tarry monocarboxylic acids likewise give a-carboxyalkyl- products. a-Halovinyl ketones and esters react to yield phosphonate~~~(19). the corresponding phosphonic acid esters.64 In an in- P(ORh teresting variation, 2,2’-dichloro-2,2’-azopropane(29) R’OOC-CHz-ha1 R’OOC-CHz-PO(OR)2 also has been recently reported65to give an Arbuzov 19 product. Isocyanide dichloride53and imidochlorides” may also CI Me be used in the reaction, the former reacting at room temperature to give carbonimidoylbisphosphonates(20). / Me U 29 I I /OEt 60% Saturated a-chloro/bromo ketones and aldehydes, /pOEt however, give the normal Arbuzov product only as a 0 minor product of the reaction. On reaction with trialkyl phosphites, the a-chloro/ bromo carbonyl compounds 20 are known to give a P-0 bond rather than P-C bond. Chloroformic acid esters yield phosphonoformic acid This mode of “anomalous reaction” is known as the esters.55@Phosphonoformamide ester is obtained from Perkow reaction,% the products of the reaction being carbamide acid chloride57whereas phosphonothioform- dialkyl vinyl phosphates. In this reaction also the first amide ester is obtained from thiocarbamic chloride.58 step, namely, the formation of the intermediate product, Michaelis-Arbuzov Rearrangement Chemical Reviews, 1981, Vol. 81, No. 4 419 is also the same as in Arbuzov reaction, involving nu- reactants, one or both the halogens may be replaced.76 cleophilic attack of phosphorus on the carbon atom. Chloroform does not react with triethyl phosphite even The intermediate then "decomposes" to give the under drastic condition^,^^ but carbon tetrachloride 30 formed by nucleophilic attack (on the reacts surprisingly readily, though only one chlorine gets phosphorus) by the carbonyl followed by di~placed.~~This reaction is accelerated by UV irra- normal Arbuzov elimination of alkyl halide; conse- diation or peroxides and proceeds via a free-radical quently the normal phosphonate (31) is not obtained. mechanism.79 However, CC14 is known to react with triethyl phosphite via both radical and nonradical pathways.8o Interestingly, phosgene immonium chloride gives tris(alky1phosphonic acid) esterss1 (35). Arbuzov intermediate

\ 35 R= Et; R',N = Me,N, N-morpholinyl 'OEt 31 30 Earlier claims regarding the synthesis of methane- With cy-chloro/bromo ketones both the normal and triphosphonic acid ester derivatives could not be veri- abnormal products are obtained; e.g., with substituted fied by later experiment^.^^^^^ cy-bromo The yields of 33 decreased Simple aryl halides are very unreactive toward the Arbuzov reaction. Iodobenzene is reported react R' to with I trimethyl phosphite on photolysis at 60 OC to give the Arbuzov product 37 by a free-radical mechanism.84 Ph. Perkow is the phenylating species in this reaction. 0 ll/OR 0 0- .P 60' (MeO)3P I/oMe 'OR Ph-1 I*+ Ph' Ph-P\ I -PhololySlS - 32 OMe 31 Q R' COCH 2B r I Ph-NZN-CPh3 t other products 38 The decomposition products of (pheny1azo)tri- phenylmethane (38) in trimethyl phosphite also yields 37; here the yield of 37 is 96-99% of theoretically 33 available phenyl radical.% Iodobenzenes have also been shown to react rapidly with potassium dialkyl phos- and 32 increased in the order R' = MeO, Me, H, F, C1, phites in liquid ammonia under "350-nm" irradiation Br, NO2. to give the Arbuzov product dialkyl arylphosphonates However, cy-iodo ketones give the normal phospho- in about 90% yield.% nate~'~~'~(and not phosphate) as the main product of the reaction. The reason for this normal behavior is the I lesser electronegativity of iodine exerting a smaller polarization effect as well as its greater reactivity toward simple displacement. Other chloro ketones and poly- halo ketones behave abnormally toward the Arbuzov reaction because of the polarization induced on the Activated aryl halides, especially those having het- carbonyl group by the electronegative halogen atoms. erocyclic nuclei such as acridine, thiazoles, quinoxaline, The formation of phosphonates is also favored by car- isoxazole, coumarin, and tetrahydrofuran systems, have rying out the reaction at higher temperature^.^^ been sed.^^?^ 2,4-Dichloroquinazolinessg(39, 40) and Chloranil(34) reacts in an interesting way with the 41 react preferentially at the 4-position. trialkyl phosphite esters of secondary alcohols, as shown in eq 4.75 Methylene and other dihalides react normally LI

CI Cl Cl 39 40 41 In 40, the C1 atoms at Cz and C4 were replaced si- 34 multaneously by the incoming phosphonate group; i.e., but less readily, and depending on the ratio of the a diphosphonate was obtained. 420 Chemical Reviews, 1981, Vol. 81, No. 4 Bhattacharya and Thyagarajan SCHEME I. Synthesis of Phosphonate, Phosphinate, react6 with alkyl halides with exchange of R. Com- and Phosphine Oxides pounds of structure 49, however, undergo ring open- 0 ing46i92to form 50 which upon heating gives rise to the ring by by cleavage of an alkyl halide.

44 (phosphonate)

45 (phosphinate) The dioxaphosphorinanes (52) react as in eq 6.

46 (phosphine oxide)

l-(Chloromethyl)-5,5-dimethylhydantoin(42) is re- 52 portedg0to react in the usual manner to give 43. Of interest is also the reaction of diazaphospholines (53) which give the Arbuzov product 54 on reaction with alkyl halide.93

Ac-N-N -ROH Ac-N-N RCI Ac-N-N reflux

42 43 RO/ Me 53 R= Me, Et 54 B. Tricoordinate Phosphorus Reactant Similarly, l-phos~ha-2,6,7-trioxabic~clo~2.2.21octane The general structure of the phosphorus ester may (11) reach-with allyl halide to give an Arbkov product be written as ABP-OR where A and B may be primary (55) ,34,35,94 alkoxy, secondary alkoxy, aryloxy, alkyl, aryl, or di- alkylamino groups. As the reaction involves nucleo- philic attack of the unshared pair of electrons of the OkI phosphorus on the alkyl halide, it is retarded if A, B are electron-attracting groups and accelerated if they are electron-repelling groups, the ease of reaction in- creasing in the order A, B = aryloxy < alkoxy < aryl < alkyl < dialkylamino. The R should be aliphatic for the reaction to proceed 11 55 smoothly. If A and B in the phosphite ABP-OR are As only one alkoxy group of a phosphite participates alkoxy groups, then a phosphonate (44) is obtained; when one is alkoxy and the other is alkyl or aryl, then in the reaction leading to phosphonates, it could be expected that partial esters of phosphorus acids and (45) If both A and B are a phosphinate is obtained. esters of amidophosphorus acids would react in the alkyl or aryl groups, then a tertiary phosphine oxide (46) same way. These variations of the reaction were de- is obtained on rearrangement (Scheme I). When R is veloped by Michaeli~.~~~~~ alkyl, then in the reaction with CH31, the reactivity of mixed trialkyl phosphites decreases with R in the se- The dialkyl acid phosphite salts also react quite quence16 Me > Et > i-Pr. Triaryl phosphites do not satisfactorily in an Arbuzov-like manner; e.g., dibutyl undergo the Arbuzov rearrangement as such, though 1-decanephosphonate (57)97 is prepared from decyl they isomerize on heating with alcohols at higher bromide and 56 as in eq 7. (This reaction is somewhat temperaturesgll (eq 5). 0 II (HsC40)2P-ONa t CIOHZ,Br -~o~rCI~HZI-P(OC~H~)~ (7) 56 57 similar to the photochemical reaction of iodobenzene R= Pr with dialkyl phosphite salts%). The synthesis of the bis(diethy1amide) of methane- Cyclic phosphites of structure 47 and 48 generally phosphonic acid (58)% provides an example of the use of amidophosphites. 0

48 47 58 Michaelis-Arbuzov Rearrangement Chemical Reviews, 1981, Vol. 81, No. 4 421 In the general category the reaction of methylol de- cently hydroquinone,lWphenothiazine,% and even acetic rivatives of acyl amides to give 5ge8and the reaction of acid 65 have been used as catalysts. 0 An examination of a series of trialkyl phosphites FC II showed12 that heating them at 120 "C for 16 h did not RCONHCHPH -& R-C-NH-CH2 - R-C-NH-CH2 bring about any isomerization. However on heating at I I 200 "C for 17.5 h the trimethyl phosphite underwent C12P-0 c1$=0 100% conversion into dimethyl methanephosphonate, 59 the ethyl ester remained stable, the isopropyl ester H 0 underwent 25 % conversion into hydrogen phosphite PC13 I II and propylene, and the allyl ester polymerized. Ar3C-OH - Ar3C-O--PC13 Ar3C-PC12 Thus it could mean that a trialkyl phosphite by itself 60 does not undergo the rearrangement to the phosphonate triarylcarbinols and PC13 to give triarylmethane- unless the necessary phosphorus compound or some phosphonic acids (60)M8~~~1''''can perhaps also be in- other catalyst (like alkyl halides) is already present in cluded. the system in small amounts as an impurity.lW Dialkyl phosphorochloridates (61) are known to react with 1-chloroethyl alkyl ethers to give the Arbuzov I v. Synthetic Applications product 62.1°1 Silyloxymethyl derivatives of phos- The Arbuzov reaction is the most widely used and versatile method for the formation of carbon-phos- phorus bonds. Some of the most important classes of compounds prepared through this reaction are reviewed below. 61 62 A. Synthesis of Phosphonates phonites (63) are also known to give Arbuzov product This is perhaps the most important class of com- 64 on reaction with halides and hydrolysis, in 91% pounds prepared by the Arbuzov rearrangement. The yield.lo2 original observation that alkyl halides reacted with 0 ,CSiMe3 trialkyl phosphites to give the phosphonate esters 44 Cl-CH$H$N_ 11 Me5SiOCH2- P, HC-P-CH? CH 2CN (see Scheme I) was found to hold good for a wide variety OSiMe3 I of substituents on both reactants. These have already CH20H been described in section 111. Earlier work regarding 63 the synthesis of phosphonates has been reviewed.'l* 64 Generally the reaction is carried out by heating the Of interest also is the reaction of the phosphonite 65 phosphite and alkyl halide to the required temperature to give the Arbuzov product which cyclizes on reaction until the reaction is complete. The reaction mixture with the base to give 3-hydroxy-2-phospholene1-oxide is then usually subjected to fractional distillation. (66).lo3 When the alkyl group of the phosphite and the halides 0 are identical, only one phosphonate is formed. Where the alkyl halide employed is not identical with the one eliminated during the second stage of the reaction, a mixture may be formed. Even so the reaction can be 65 controlled to give the desired product. In such cases it is decidedly advantageous to distil the alkyl halides generated during the reaction itself; for example, in the reaction of 1-chloromethylnaphthalene (67) with tri-

,OEt CH2CI CH2-P 66 I I II'OEt a, PhCH,, R' = Ph R= OEt; 150-60 OC b, R = Et, OEt; R' = COOMe t (EtO13P --EtCI (in small excess) C. Effectiveness of Catalysts 67 87 % Normally the Arbuzov rearrangement proceeds ethyl phosphite"' the more volatile ethyl chloride without the help of catalysts, but in some situations formed during the reaction is continually distilled until catalysts are needed. For example, the reaction of io- the reaction is over. dobenzene with trialkyl phosphites does not proceed When the alkyl halide employed and that formed under normal conditions but may be photo- during the reaction are of more or less the same re- cataly~ed.~*~*~~Certain metal halides also serve as activity, the control of reaction may be aided by the use catalysts. Thus the reaction of triethyl or triisopropyl of a large excess of the reactant. Thus when a mixture phosphite with a number of unsaturated alkyl halides of 5 mol of trimethylene bromide and 1 mol of triethyl or aromatic halides is accelerated by nickel halides or phosphite is refluxed under a fractionating column (for copper powder. An even better catalyst is palladium the removal of ethyl bromide as it is formed), the ester chloride.62J04-1mOther nickel and cobalt saltslo8such of bromopropionylphosphonic acid is obtained in 90% as Ni(C0)4and C0C12 have also been used. Very re- yield.l12 422 Chemical Reviews, 1981, Vol. 81, No. 4 Bhattacharya and Thyagarajan In all these reactions, some complications might arise gives 2-oxopropylphosphinates (70)'38J39as the major due to the self-alkylating ability of the trialkyl phos- product, with a minor quantity of 69. phites. Thus phosphonates are also formed during heating of trialkyl phosphites, especially in the presence of catalytic amounts of , alkyl halides, aluminum alkyls, inorganic iodides, or thermally from Cu(1) ad- duct~.~~ Solvents are, in general, not used, but sometimes they help better reaction control. An example is the internal Arbuzov rearrangement of 3 to 4, where the use of hy- drocarbon solvents gives better re~u1ts.l'~ Et0" \CHz-C--Me II B. Synthesis of Phosphinates 0 70 The dialkyl also undergo Arbuzov re- arrangement on treatment with alkyl halides, resulting The acetals of a-haloacetaldehydes and those of p- in the formation of phosphinic acid derivatives 45 (see halo aldehydes react normally to give the acetals or enol Scheme I). This is a major route for the synthesis of e~ters,~~OJ~~and these can be converted easily to al- the esters of alkylaryl- and unsymmetrical dialkyl- dehydoalkyl phosphinates. However, a-haloacet- phosphinic acid derivatives. The majority of the re- aldehydes themselves yield vinyl esters of phospho- actions which have been described involved unsubsti- nates. tuted saturated or unsaturated aliphatic or side-chain There are examples of some unusually substituted aromatic halides and unsubstituted phosphonites and halides which, however, undergo the normal reaction, therefore give products which contain only hydrocarbon e.g., phthalimido a variety of silicon-containing groups. However, all the halides capable of undergoing ~ubstituents,'~~sulfonyl fluorides,lU sulfonate ester SN2 displacements may be used in this synthesis, and gfo~ps,'~and butyl bis(chloromethy1)phosphinate (71), a variety of substituents may be used in the phos- yielding the triphosphinate ester 72." phonite too. The reaction of a phosphonite with a dihalide may result in the formation of either esters of haloalkyl- phosphinic a~ids"~J~~or of diphosphinic acids.""'18 The latter can also be prepared by the reaction of alkyl halides on diphosphinite~.'~~Similarly the reaction of 71 diphosphonites and dihalides yields poly- phosphonites.'2fl Likewise, w-haloalkyl phosphonite 72 esters yield cyclic phosphinates'21J22(68) by intramo- There are many examples of phosphonites with allyl- lecular rearrangement; e.g. and benzyl-type halides, but examples involving sec- CHz-CHr-CI OC4H9-P 165j-1,0.c CHz-CHz ondary or tertiary halides of any kind are limited to I / -n-C4HgCI I \P4O reactions of isopropyl iodide,48dimethylphenyl chloride CH2-Crl2 "\OC4Hyn CH2-CHz' \oc4p9 and br~mide,'~lJ~~triphenylmethyl bromide,148and a 68 few other substituted secondary or tertiary hal- These reactions are typically carried out by mixing ~~~S.'~J~~JQ'@Even more limited are examples of vinyl the phosphonite and the halide at room temperature, halides: perflu~ropropene'~J~~which reacts at the heating the reaction mixture slowly, controlling the 1-position, 1-chloroperfluorocyclopentenewhich reacts reaction in case it tends to become vigorous, and finally with the replacement of the 2-fluor0 atom,1521-2-di- maintaining the reaction at 120-160 OC for several chloroperfluorocyclopentene in which both chlorine hours. The yields are generally around 80%, but atoms are replaced to give a diph~sphinate,'~~and 1- sometimes overheating causes some pyrolysis of the cyanovinyl bromide'54 (a-bromoacrylonitrile), and ester to acid,123and consequently lower yields. benzenesulfenyl- and phenyl sulfonylvinyl bromides155 In dialkyl phosphonites, the R directly attached to which, whether 1- or trans-2-substituted, react to give phosphorus is known to contain halogen-substituted trans-2-substituted products. aromatic,'24dialkylamin~,'~~ and keto and ester group- There is one instance of an Arbuzov-type reaction ings,la6but in general the substituted phosphonites are with a diary1 ph~sphonite'~~in which a quasi-phos- not easily available. The R of the alkyl halide, the other phonium intermediate forms readily, but because it is reactant used in the reaction, could contain functional very stable, an alkaline hydrolysis is necessary to obtain groups such as alko~y,'~~-'~~alkylthi~,'~" acyloxy,lz8 the aryl phosphinate. With carbon tetrachloride the carboxylic e~ters,~~J~~J~'tertiary car- phosphonites also react, apparently by a free-radical bothiolic ester,'% nitrite,'% and tertiary amino group^.'^ mechanism, as in the case of the reaction of phosphites However, groups such as hydroxy, thiol, carboxylic acid, with CC14$ either at room temperat~re,'~~during 20 and primary or secondary amines are not to be found min on a steam bath:32 or on refluxing at 70-80 0C.158J58 for the simple reason that these substituents themselves Sometimes Arbuzov reactions proceed without ad- reacts with phosphonites. dition of halides, but they are probably catalyzed by the Due to their high reactivity, acyl halides react at impurities during the distillation of the phosphon- much lower temperatures, yielding esters of acyl ites.160J61True uncatalyzed rearrangements of ordinary phosphinic a~ids.'~~,'~~Chloroacetone yields (615% ) pure phosphonites occur at 240 "C or higher.162 How- isopropenyl phosphonates (69)'%whereas bromoacetone ever, 2-chloroalkyl esters of phosphorus acids get isom- Michaelis-Arbuzov Rearrangement Chemical Reviews, 1981, Vol. 81, No. 4 423 erized to 2-chloroalkyl phosphinates (73) around 150 phosphorus ester reaction^,^ this reaction would be O C.163-165 difficult. The reluctance of aryl groups to undergo nucleophilic substitutions hinders the formation of phosphine oxides. Thus, it is reportedlo8that phenyl diphenylphosphinite reacted with methyl iodide to give a solid (77) which was quite stable to heating. 73 Ar= C,H,,p-CIC,H,,p-MeOC,H,,etc. Ph\ P-OPh -Ma1 Me\Ph-P-OPh Ph/ Ph/ i The conversion of the 1,3-dichloro-2-propyl phos- phonite (74) into 2,3-dichloro-l-propyl phosphinate 77 7P6provides evidence for the formation of a quasi- Me\ t 76 Ph-P-OMe -t other products phosphonium intermediate 75: must have been Ph' I_ formed through the intermediacy of 75. 78 (CIHzC)zCH (CICH2)zCH I -I Pyrolysis of 77 resulted in the formation of 78, io- ,o dobenzene, and an unidentifiable solid. Other phen- oxyphosphonium salts have been transformed into Hz CHL 'Et phosphine oxides by treatment with water178 and aqueous base179or by heating179(eq 8).

74 75 \+ base heat \ -P-OAr - -P=O t ArOH t HX (8) X- or wafer /

0 It is worth noting that the alkyl halides R'X which are frequently produced during the reaction are capable /r\ CHz Et of alkylating the starting esters. In such cases a mixture

I of phosphine oxides is produced which makes the CI-CH-CH2CI workup procedure complicated. 76 Some phosphinite esters undergo "self-isomerization" to the corresponding phosphine oxides; in other words Allyl phosphonites are rep~rtedl~J~~to isomerize to they get isomerized even in absence of halides (eq 9). allyl phosphinates during distillation or upon heating to 110-140 OC. During the thermal rearrangement of phosphonous and phosphinous allyl esterP8 there is interconversion of 1-methylallyl and but-2-enyl groups. Likewise crude alk-1-ynyl phosphonites rearrange at room temperature to give alka-1,2-dienyl phosphi- The isomerization may be effected by heating and is The above instances also point to the catalyzed by impurities present in the reaction mixture formation of cyclic transition states in these reactions. or by the addition of small quantities of iodine or alkyl halides.175 In fact, it is quite often difficult to isolate C. Synthesis of Tertiary Phosphine Oxides the phosphinite ester because of the ease of its further isomerization. Thus earlier attempts175 to prepare A convenient route to prepare tertiary phosphine methyl and benzyl diphenylphosphinite failed as they oxides 46 consists in the reaction of phosphinite esters resulted in the formation of phosphine oxides. with alkyl halides (Scheme I). In general, the phos- Some allyl 79 are very reactive to phinite esters undergo the Michaelis-Arbuzov reaction thermal self-isomeri~ation;~~J~~~~so are the 2-alkynyl quite readily. Ethyl diethylphosphinite reacts with phosphinites 80.32J69Js4J85On the basis of extensive ethyl iodide at 45 OCand within 5 h. Methyl iodide experimental evidence, the mechanism of self-isomer- reacts very vigorously even at room temperature to yield ization of these esters has been shown to involve con- diethyl methyl phosphine oxide.174 Aryl-substituted certed intramolecular processes (eq 10, 11). In this phosphinite esters such as methyl diphenylphosphinite appear to be less reactive than the alkyl analogues, since 0 R' their reaction with methyl iodide could be ~0ntrolled.l~~ A wide variety of alkylating agents have been used in the reaction: primary and secondary alkyl chlorides, bromide, and iodides, a-halo ketones, a-halo esters, a-acetyl chloride, bend chloride, ethyl chloroformate, 79 ,-. triphenylmethyl bromide and cycloalkylvinyl halides.176 \il It has been shown, by using differential thermal 'P'U PC -.. ,P--CH=C=CHz (11) analysis, that the ease of rearrangement for various ''P-CHz / sub~tituents~~~J'~is 2-alkynyl > 2,3-alkadienyl > 2- alkenyl > alkyl. 80 The reaction in the latter case has been shown to be self-isomerization the classical phosphonium interme- intermolecular and is catalyzed by alkyl halides. diates are probably not involved, and, therefore, they Aryl halides do not seem to react with phosphinite are somewhat different from the classical Michaelis- esters. It is expected that, by analogy with other Arbuzov reaction. 424 Chemical Reviews, 1981, Vol. 81, No. 4 Bhattacharya and Thyagarajan The scarce availability of the starting phosphinite dichlorides have not been isolated in the reactions as esters acts as a limiting factor in the synthesis of the the products are directly hydrolyzed to the phosphonic phosphine oxides. It has been reportedle6JWthat these acids. (Hydroxymethy1ene)camphor also reacts in an esters could also be obtained as in eq 12 and 13, which analogous manner.lW increases the scope of this reaction. The alkyl phosphorodichloridates 85 react at elevated temperature in the presence of alkyl halides.2w203 / cI ~RzN-P t 2R'jAI \CI -2AIC13

85 High overall yields of phosphine oxides are obtained Nickel iodide or ferric chloride catalyzes the reac- when unsaturated alcohols, functionally substituted tion.m1*202Phosphonofluoridite esters (86)204also react alcohols, and a,w-alkanediols are employed (eq 14). similarly.

86 In the presence of ferric chloride as catalyst, even functional alkyl halides 87 have been reportedm5 to react with 85. 0 Ip 85 t CICH2NCO - ONC-CH2-P (15) -R'CI \CI 81 81 In a variation of the reaction, halogen has also been Several novel compounds containing up to four used206instead of alkyl halide (eq 16). phosphorus atoms have been preparedla7-lQ3in high 0 yields by the use of the Michaelis-Arbuzov phosphinite reaction, for example, 82.

R E. Other Synthetic Applications 'P-OR' + / R The usefulness of the Michaelis-Arbuzov rearrange- ment in the synthesis of phosphonolipids which are 82 more stable than phospholipids in the body fluid is attracting much attention in chemotherapeutic re- D. Synthesis of Phosphonyl and Phosphlnyl search. The procedure followed207is depicted in Halides Scheme 11. Besides the phosphites described earlier, certain The conversion of (2-phthalimidoethy1)phosphonic trivalent phosphorus compounds of the type 83 also acid (88) into phosphonolipids is known in the litera- undergo the Michaelis-Arbuzov rearrangement. ture. Certain alkyl halides which are not otherwise readily 7 accessiblels can be made by the Michaelis-Arbuzov rearrangement. An example is neopentyl halide (eq 17).

ArO \ ArO 83 Z=OorS ArO-P t R'-hal- ArO / Though catalysts are required,"J* the isomerization is also known to take place without them. Propargyl 89 esters 84 for example, rearrange readily.lW-lQ8 Aro\pHo + R-ha1 (17) /\ ArO R' The phosphonium salt 89 is quite stable. If it is treated with an alcohol, an aryloxy group is replaced by an alkoxy group, followed by the rearrangement in 84 the normal way. N-Hydroxymethyl carboxylic amides yield normal The Arbuzov rearrangement has also been used as a alkyl phosphorodichloridates, ROPC12, on treatment new means of synthesis of sulfonophosphono ethylenes with PC13. On prolonged standing the ROPC12 isom- (90) and diphosphonoethylenes (91)208(Scheme 111). erizes to phosphonyl dichloride, warming with acetic The rearrangement is also used in the preparation of anhydride favoring the reaction. Specific phosphonyl the starting materials (phosphonates) needed in the Michaelis-Arbuzov Rearrangement Chemical Reviews, 1981, Vol. 81, No. 4 425 SCHEME 11. Synthesis of Phosphonolipids as a nucleophile, resulting in the cleavage of the sul- 0 fur-phosphorus bond to form 92 and 93. B. Alkyl Phosphonodlthloltes Dialkyl phosphonodithioites react with alkyl halides at 130-150 "C to give, by rearrangement, dialkyl 0 phosphinodithioates (94) as the major product together

R'S\ n R'S\P-R" i + R'X P-SR' + R"X - R' R/ 94 HO\Il P-(HzC),-N'D - - phosphonolipid with a variety of other minor products. A number of / 'c phosphinodithioates have been prepared in this man- HO I1 ner.213-216 0 88 C. Phosphlnodlthloltes SCHEME 111. Synthesis of Sulfonophosphono- and Phosphinodithioites are also known to isomerize into Diphosphonoethylenes phosphine sulfides (95) under Arbuzov conditions176(eq /S02R appropriate trialkyl 18). The reaction has not been investigated in as much HzC=C + phosphite or dialkyl - \Br phosphonate R 0 R >P--SR 'P-R R' appropriate - \I1 phosphite I R R' ,P-CH=CHSOzR or O=P-CH=CH-P=O R" phosphonite I I 95 R"' R" 91, R=MeO, Ph, Et0 detail as that of the oxygen analogues-the phosphin- R' = MeO, Ph, Et0 90, R = Ph, PhCH,, Et, Me R" = MeO, Ph, Et0 R' = MeO, EtO, Ph ites. The mechanism is believed to be similar (eq 19, R"' = MeO, Ph, Et0 R' = MeO, EtO, Ph 20). s Homers-Wadsworth modification of the Wittig reac- R n R\II tionZm and in the structure determination of tri- \P--SR' - /P-R' phosphites of D-r"itOl and DL-Xylitol.210 The cyclic R/ R phosphites are heated with ethyl bromide under Ar- S buzov conditions, and on the basis of the structure of the phosphonate obtained, the configuration of phos- phite of the hexose can be determined. Perhaps due to the lesser strength of the carbon- V. Behavior of Sulfur and Fluorine Analogues sulfur bond as compared to the carbon-oxygen bond, under Arbuzov Conditions the rearrangement of the sulfur analogues is more rapid than that of the pho~phinites.~~~*~~~The intermediate A. Trlalkyl Trlthiophosphltes phosphonium salts also can be isolated if the reaction is carried out at low temperature.219 Trialkyl trithiophosphites are reported211to react by In a similar manner alkyl phosphonamidothionites a mutual exchange process which is in sharp contrast (96) also rearrange to phosphine sulfides on reaction to the behavior of trialkyl phosphites. The mutual with alkyl halides. 220 exchange process has been applied for the synthesis of thiophosphorochloridites (92) and dichloridites (93). EtS (EtS13P + RCI '40-'500L \P-CI + RSEt EtS/ 96 92 D. Organofluorlne Compounds Under Michaelis-Arbuzov conditions alkyl fluorides 93 and phosphites react to give abnormal products221(eq Triphenyl trithiophosphite also reacts similarly.212 A 21). explanation could be that as the sulfur atom has vacant 0 d orbitals (unlike the oxygen which has none), it could enter into a partial double bond formation with the I1 unshared pair of electron on phosphorus. Consequently the unshared electron pair is localized more toward sulfur, making it more nucleophilic than phosphorus. The electron-rich sulfur now attacks the alkyl halide MeO/ 'CF3 426 Chemical Reviews, 1981, Vol. 81, No. 4 Bhattacharya and Thyagarajan SCHEME IV. Abnormal Reaction of Fluoro Compounds Nitro groups are usually reduced by tervalent phos- with Trialkyl Phosphites phorus esters, but o-dinitrobenzene is known to react F with diethyl methylphosphonite to give an o-nitro- ,CF3 /cF3 [RO'sP phenyl phosphinate (99).232Nitro olefins are also re- FzL=C. -- (RO)jP--C=C ported233to react similarly with trialkyl phosphites in \COR j \COR F an Arbuzov manner, yielding 100. 97

(not formed) 0 a, R= Me, Et; R' = Me 99 = = b, R Et, Me; R' Et 0

Fluorinated ketones also react unusually with silyl R'-CH=CH-N02 'P-CH -CH2--NO, and acetyl phosphites222(eq 22, 23). RO' I R' -.o 100 F--:: bile3 + Fjb---- -'3- -- R= Me, Et, Pr, Bu; R' = H, Me L +c' /I i Hydroxymethyl amides are also known to react with phosphites in the usual manner, e.g., 3-bromo-N-(hy- droxymethy1)benzamide (101) reacts with trimethyl phosphite to give the phosphonate.234 0 0 OAc II,o'e II,o'e CONHCHzOH CONH-CHz- P I I \OMe EtO' II 0 C. F3 Perfluoromethacrylic acid forms an adduct (97) with trialkyl phosphites which splits in an abnormal wayzz3 101 (Scheme IV). Free radicals are known to bring about the rear- Very recently polyfluoroaromatic compounds con- rangement of phosphinite esters to phosphine oxides. taining activated fluorine atoms have been reported to Thus, dimethylamine radicals initiated the chain re- react in the Arbuzov way with trialkyl phosphites.224 action for the conversion of methyl diphenylphosphinite (102) into methyldiphenylphosphine and of VI. Rearrangement of Phosphites in the Presence of Compounds Not Contalning Halogen Generally the presence of alkyl halides is essential for the rearrangement as they enter into a reaction with 102 (initiation) phosphite forming the phosphonium intermediate 0 which then splits in the Arbuzov manner. However, rearrangement is also known to occur in the presence of reactants which contain no halogen. Thus dialkyl sulfates,16 alkyl p-toluenesulfonates,zz5alkyl fluoro- cyclic phosphites into phosphonate~.~~~ borates, and lactones also react with trialkyl phosphites Methyl and isopropyl radicals generated by the in the usual manner to give 98.zz6~227 photolysis of azoalkanes reacted with 102 to yield methyl-(33%) and isopropyldiphenylphosphine oxide 1 (80%).236 Benzyl radicals were found unreactive whereas tert-butyl radicals236merely initiated the re- arrangement reaction. Phenyl radicals gave tri- R -C H-c H~- c H~-COOR phenylphosphine oxides in moderate yield when reacted I /OR with various alkyl diphenylph~sphinates.~~~ o=P Tricarbonylcyclohexadienyliron tetrafluoroborate '0 '0 R (103) has been recently reported237to react with tri- 98 methyl phosphite to give the Arbuzov product 104. Other alkylating and acylating agents which react Reaction with FeC13 is known to remove the tricarbonyl according to an Arbuzov scheme are lactams,226~228 iron group from 104. sulfones,229salts of Mannich bases,230and carboxylic 103 reacted with aqueous hypophosphorus acid (2 h, acid anhydride.231 65 OC) to give the phosphinic acid 105, converted to 106 Michaelis-Arbuzov Rearrangement Chemical Reviews, 1981, Vol. 81, No. 4 427

R AB-17 MeOH R' Me 111 112 103 R= R' = alkyl, alkoxyalkyl; R" = C1

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