#FOS)- P. 040&

" INORGANIC SULFUR REAGENT3; I THE THIONYL HAUDES

By

Charles M. Buess, Norman Kharasch and Robert B. LangfordChemist~ry Department, L~niversity of Southern Califor

. Los Angeles 7, California

Our studies of organic sulfur compounds have made us increasingly

aware of the inorianic sulfur reagents, While it is clear that many compounds

of this group have now become of greatest theoretical and practical interest,

yet there has been a lack of correlative and review papers which would serv6

to focus attention on them. Since we had much of the required literature at

hand. it seemed desirable to prepare a series of brief articles, each of

which would give a thorough entry to the literature on a selected group of

m these substances.

The present paper concerns the thionvl haiide , SOX2 . The known

examples of this group of compounds are shown in Table I, together with the.

other known compounds of sulfur and halogen, and of sulfur, oxygen and

halogen. Part II of this series will present the sulfuryl halides, SO2 X2 .

THIONYL CHLORIDE

Iv Physical Propertie.Thionyl chloride, SOCd, melts at -104.5°, boils at 78.80, has a

density (at 14. 50) of 1. 656 g./ml. and a refractive index, n1, of 1. 517 *

Pure thionyl chloride is a colorless, fuming, toxic, irritating liquid

which in miscible with benzene, carbon tetrachloride, chloroform and most

inert organic solvents. Studies involving force constants, , infrared, , 6

Raman, 7-10 and ultraviolet spectra, magnetic rotatory power, 12 magnetic

susceptibility13, and dielectric constants and dipole moments 14 ' 15 have been

carried out. Its physical properties have suggested its frequent use as an

ionizing solvent. The heat of formation of thionyl chloride in -58.5

Xcal. /mole. 2 1

The first preparations of thionyl chloride employed the reactions of

Podium sulfite with phosphorus pentachloride22 and of calcium sulfite widti

phosphorus oxychloride.23 Industrial methods, described in the "ID C

Uterature, 25=31 have sought less exp~nslve syntheses, exam /I

are shown in the following equations: SEP 3 0 19•5

* This review was prepared In conjunction with studies suppOffice of Scientific Research, United States Air Force, ContractAV' Aa-ffl..71A .- A &I.-n Qbf..tt..q r~ - - %ft

(az4,3s "SbC13.(-1 sci. +so 3 so + soca,

(2) 25 S C 2 + 2 S0o + 3 C 1 2 S 4 SOC,

(3)26 Co + $02 2 s SOCIZ + COC

(4)27 2S + 0 + 2 CL - catalyst 2 SOC12,

2s68. 9 so +coC 1G3(5), s20 + CCI SOCh + ('OC12

In the process of equation 1. sulfur dichloride may be prepared.insitju

from sulfur monochloride and chlorine (CISSCI + Cl -- Z CISCI).

The sulfur trioxide is usually intro&dced by using fuming sulfuric acid.

Excess sulfur trioxide must be avoided because of the easy formation of the

so-called 'lyrosulfuryl chloride" (equation 6). If radioactive SCIZ is used

(6) SOC12 + 2 so03 S-osC1Z + SOZ

in th method of equation 1# the tagged sulfur is found mainly in the thionyl

chloride. 32

Considering the reaction of equation 2: sulfur dichloride may be

substituted for sulfur monochloride and part of the chlorine, and sulfuryl

chloride may be used as a source of SO2 and %;I,. The reaction is best

carried out at 150-2000. With recycling of the sulfur chlorides. SO2 and

SOCl. which are formed, nearly 100%, cunversion is reported. At hightemperatures (500°), the decomposition of thionyl chloride is nearly complete.

At intermediate temperatures (1980 and 2380). the system. SOzC12 + SCI!

2 SOCI 2. represents & reversible reaction. 3 0 The oxidation of SCI, with

oxygen, to give sulfuryl chloride is Irreversible under these conditions.

Equation 7 represents an overall procedure which has been used to prepare

thionyl chloride. 3 0

(7) a SC)Iz + 03 C(activated) z SOC12

Phosgene may also be employed in reaction 3.

Is reaction 5, the yield of thionyl chloride is 72%. Substitution of

chloroform or pentachioroethane for carbon tetrachloride lowcre the yield

to 40% and 6%, respectively.

aia This chlorinolysis of the sulfur-sulfur bond Is a very general reaction.

and has found many applications in organic chemistry. The productsobtained are sulfenyl chlorides: 2 RSSR + Cl. -. 2 RSCl. Cf. e.g.,Organic Sulfur Compounds, Vol. 1. edited by N. Kharaschg PergamonPress (1960): Cho. 31 .and 12.

-m3-

The reaction of boron trichloride with the sulfur dioxide, in which thelatter acts as solvent, is extremely slow unless chloride ion is present. 3 3

It has been suggested that the catalytic effect of chloride ion may involve

the iot, SOaCl"

(8) Z C13 + 3 502 - 3 SoC12 + BZ0 3

Technical grade thionyl chloride contains about 7% impurities, mainlysulfur monochloride, sulfuryl chloride and sulfur dioxide. 3 4 Sulfurmonochloride may be removed after reaction with sulfur, and the sulfurylchloride may be taken out by means of its selective reaction with othersubstances. 3 4 Reagent grade thionyl chloride is also available.

Chemical Properties

Above its boiling point, thionyl chloride decomposes to sulfur chloride,sulfuryl chloride, sulfur dioxide, and chlorine. The photochemistry of

Sthionyl chloride does not rsem to have been investigated in detail, but seemsworthy of study, especially in comparison with sulfuryl chloride.

Rapid sulfur exchange between S*OCk,-SOBra and SOCI 2 -S OBr 2 in SO2solution at -50° or in mixtures of pure compounds at -20° has beenobserved. 3 5 Similarly, chlorine exchanges rapidly between Cl!-labelledpyridinium chloride and SOCI in chloroform at Z0°. 36 These results maybe accounted for by the ionization of the thionyl halides or the formation ofaddition complexes and are in mnarked contrast to results wherein the lack

of exchange between SOClZ and SOZC12 has been noted.3 5

Thionyl chloride reacts with metals, such as antimony, sodium,aluminium, magnesium, and iron. The reactions are generally slow in

the absence of acids 37 (except in the case of antimony) and this explains theuse of iron containers for storage of the th)ronyl chloride. Glass, lead, andnickel containers are also used for storage.

With phosphorus, selenium and tellurium, reaction with thionylchloride yields the respective chlorides.

"Hydrated chlorides, such as MgC1Z. 6 H.O, are conveniently dehydratedwith SOC12, since the products, HCI and SO., are gases.39 Mustard gas40may also be dried in this way.

In some of its inorganic reactions, thionyl chloride acts as anomddising agent, e.g.:

(9) 4 HM + 2A 0CIZ----4 12 + 4 HCI + SOZ + S

(10) Z H ÷ 2 SOC1 AIC13 -) 4 HCI + SO +3S

. "4,-. - . - --

49

In other reactions. however, It functions as the reducing agent:

(11) 7. HNO3 + SOCIl - H SO 4 + NO C1 + NOCI

(12) N2 o 4 + SOC1-- ZNoCl + S03 0

The reaction with silver nitrate yields silver chloride and CISONOz,

while with ammonia, polymeric thionylimine, (HNSO)x, is reported as theproduct.41 The preparation of chromyl chloride using Cr0 3 or K. Cr0 7has been mentioned. 42

The best known reactions of thionyl chloride in organic chemistry

involv, the replacemant of hydroxyl groups. in alcohols and carboxylicacids, by chlorine. The conversion of alcohols to alkyl halides often occurs

with retention of configuration. This is not, however, always the case.The steps involved in the reaction converts the alcohol to chlorsulfinates

and. in some instances, to sulfites. Under certain conditions these

intermediates can be isolated. 0"

(13) ROH---) RO-[-l ---. R

*R0ORThe elimination of sulfur dioxide from the chlorosulfinates may occur throughdifferent transition states.

The detailed mechanism and stereochemistry has been studied in a

number of Investigations with alcohols, 32, 46, 47, 48 with small ring alcohols 4

with chlorocyclohexanols, with allylic alcohols, 51 with acylamino alcohols$2

and with sterols. 5 3 , I The widely used reaction for conversion of acids to

acid chlorides has been shown to occur through the carboxylic anhydride

when pyridine in employed. 5 Sulfonic acids and carboxylic acids, which

do not normally react with thionyl chloride, do so in the presence of

dimethy1formamide.5 6 The ionized salt (CH 3)zNCHCl+CI', isformed. Another Interesting application involves the estimation of the

number of carboxyl groups in gelatin with SOC12 and CH 3 OH. 57 2-Naphthoic

acid, heated with thionyl chloride at 180-2000, yields 1, 6-dichloronaphthalene.Mercapto groups are replaced by chlorine and some ketones are converted to

vinyl chlorides by SOCIZ. 59 Ethylene oxides yield Z-chloro sulfite.6o whileA 61

aliphatic A -lactones give 3-chloroalkanoyl chlorides.

(12) 1 H C - CH + 30C1 2 4 (CH ClCH 0430

(13) CH CHzOCO +SOCk - CH . CH COC1 + so 2

Thionyl chloride cleaves cyclic ethers and related compounds toafford dichloro derivatives. Examples are the reaction with tetrahydrofuran

and 4-phenyl-l, 3-dioxane.63 AMother interesting ether cleavage involves the

(14) + sOClZ M. IClCHzCHzCl

C6 H5 65

conversion of r-methoxyvaleric acid to methyl I-chlorovalerate withInversion at the Y'-carbon atom.64

The products of the reaction of SOCI 2 with phenols are dependent on

the conditions. In some instaixces sulfites can be obtained and under otherconditions ring substitution occurs. The reactions of this type have beenreviewed. 6 5 In general, the Friedel-Crafts reaction with SOC12 is not very

successful, but 9-fluorenyl66 and a-acetamidopheny167 sulfoxide may bepreapared in this way. In the presence of copper, SOC1? and substituted

68 6phenols (4-hydroxycoumarin, 4-propionylresorcinol, 69 Zhydroxy.5-methylacetophenone, and the naphthols yield symmetrical sulfides byring substitution and attendant reduction.

Thionyl chloride is an effective agent for intramolecular removal ofthe elements of water. Examples are the dehydration of 1, 1, l-trichloro-Z-methyl-Z-propanol, which occurs A; the chlorosulflnate and which iscatalyzed by amines, 7Z and ethyl 2-carborxiethoxy-l-hydroxy-Z-methyl

cyclohexylacetate.73 The units of alcohol are similarly removed from asubstituted phthalamic acid7 4 and water is removed intermolecularly from

751 76,77oxanilic acid.* 5 Urea is converted to cyanuric acid and other products.

(15) CONR 0O ",•COOH " F 0 : O1N,

C6H5(16) COOH N11.1%

21 0m a CXOCONHC 6 H5 I0 a C / 0

C6H

The intermolecular condensation of glucose is also effected through the use

of thionyl chloride.7 8

Chlorination of compounds with thionyl chloride is illustrated by the

reaction with dimethyl sulfide.79 For these purposes, thionyl chloride Isa less vigorous *gent than sulfuryl chloride and promotes formation of monoand dichloro derivatives, rather than higher chlorinated products. The

-6addition of chlorine to benzene is activated by the presence of thionyl chloride

and the amount of the gamma isomer of hexachlorocyclohexane may be

'affected by its presence 800 8a In the special case of I1 l-diarylethyleneq,s5flnic acid is obtained 2 after hydrolysis of the product. Chloropheno

(17) Ar C a CHl 4+ SOCI.--- Ar 2 C w CHSOH

thiasines are chlorinated by thionyl chloride. 3 Alternatively, the

phenothiauine ring may be closed with the chlorination by the action of thionyl

chloride on diphenylamine.

The oxidative character of thionyl chloride in sometimes exhibited in

organic reactions. The cleavage of substituted 69,9 "-bixanthenes to

xanthones84o 85, 86 and the dehydrogenation of a highly hindered acrylic acid.cis'of :41 S-(l' a'-naphtho)-3-pyrazolyl3 cinnamic acid, to the corresponding •.

(18) / ~1) SOCl 2

* ~ III ~2) Hi2 0propiolic rcidg7 are examples.

Thionyl chloride in not usually the best reageut for effecting the

Beckmaann rearrangement because it initiates cleavage reactions.8 8 The

conversion of cyclohexanone oxime to epsilon-caprolactam with thionyl

chloride occurs with fair results, however. 89

Primary aromatic amines are converted to thionylimines. ArN a SO,with 5OC12 9 0 8-Thiapurines are obtained by the reaction of thionyl chloride

with S5 6-diaminouracils. 91 Other thiadiazoles are obtained through the ust

of orthodiamIines.9 2 The cleavage of sulfinyl esters by SOC 9 3 and its

addition to ketene to give after methanolysi. (MeOOCCH 2)2S 94 are further

interesting applicaUons. Its reaction with phenylaersine to givee C6 H5AsS9S

contrasts with the reaction of phenylphosphine with SOCIZ, which yields(C6HsPSO) 96 C6HsAs(MgBr), and SOCl 2 gives C6 HsAsSO.

A possible application of thicayl chloride. which has not been exploited

fully an yet, Is its chain terminating properties. It has been shown thatSOCI acts in this way in the sulfoxidation of cyclohexane (reaction with SO3and 029 under irradiation). 9 7

Reviews on the early chemistry of SOC12 *2 3 the reaction with phenol,, 5

with raminobensoic acid#9 synthetic applications$ and technology10 haveappeared.

"-7

THIONYL FLUORIDE

Thlonyl fluoride, SOF., melts at -129.5o and boils at -43.8 101.02lOZ10 105 105Raman, , infrared, and microwave spectra, dipole moment and

force constant stAdies have been carried out. Thionyl fluoride Is obtained

by the reaction of thionyl chloride with AsFy3 SbF 3y 106, 107 -F, 108 or

KSO2 Ft 10 9' 11 0 by reaction of S4 N4 with aqueous HF and CuO, 111 and byreaction of SO2 'with VF 5 ,112 A 77% yield was obtained recently by reactionof sodium fluo.ide with thionyl chloride in acetonitrile.13

Thionyl fluoride hydrolyzes slowly, but completely at room temperature,

furming sulfurous and hydrofluoric acid. Thel'mally, however, It is quitestable. 106 With SiS 2 at 4000p thionyl fluoride gives SiF 4 and SOV.

Mixtures of SOFa and 0., submitted to an electric discharge, give peroxy

compounds. U4

THIONY L CHLOROFLUORIDE

Thionyl chlorofluoride, SOCIF, boils at 12.20, melts at -139.50, and

has a liquid density of 1.580 g./ml.10 1 It is prepared by the action of SbF 3and 3bClI 101 or IF,.115 on SOCIZ. The chlorofluoride reacts with

mercury and copper, at room temperature, and with iron at 700. Theoverall reaction is represented by equation 19. (M w metal).

(19) 4SOCIF + 3M--2- SOF2 + SO 2 + MC12 + 2MS1

Disproportionation may occur first; if so, the products are those of the

reaction of SOC12 with the metal.10 1

THIONYL BROMIDE

Thionyl bromide, SOBr 2 , melts at -520, boils at 1380 (decompn.),

it atmospheric pressure or at 42.5° at 16 mm. press-are, has a density atISO of 2.698 and is an orange-yellow liquid.11A Raman spectrum. 117 116s 118t 119Thionyl bromide is prepared by the reaction of HBr or KBr with SOCI2.116Reports of the existence of SOC1Br are probably incorrect. Thionyl

bromide decomposes slowly at room temperature (4 SOBr 2---* S.Br 2 +2 SOa + 3 Br.) and is rapidly hydrolyzed by water. Thionyl bromideconverts carboxy-ic acids to acid bromides and substituted alcohols to thecorresponding bromides., 1 9 , 120 A general method involving conversion ofalcohols to sulfites with SOCI2 and cleavage of the (RO) 2SO .- ith thionylbromide is recommended for the preparation of alkyl bromides. 12 1 Thionylbromide reacts with pyridinium halides to give C HSNH+ XBr 2 " along vithS and SO2.12@ 123 Sulfur exchange between sulfur dioxide and thionyl

bromide Is slow124 unless ionic halides or catalysts are present.12 5 ' 126

A review of the synthetic uses of sulfuryl bremide has been made. 99

THIONYL IODIDE

Thionyl iodide, SOI., is unstable. Its formation by reaction of

thionyl chloride in carbon tetra-:hloride solution with potassium iodide, 127, 128

has been reported and Its decomposition was followed by spectroscopic means.

It is decomposed by light. Dilute solutions in the dark are claimed to be

stable for eight hours.127 It has been considered to be an intermediate in the

following reactions: 129

(20) (C2 H5 O)2 SO + 6 HI H2S + 2 C2 H5 OH + H20 + 31

(Z1 SOC1Z + 6H1- HzS + H2 0 + Z HC1 + 3 1

The results probably bear reinvestigation, since quaternary ammonium

iodides, when treated with thionyl chloride, yield malts as follows: 130

(22) 2 + 2 SoC 1 2 21 ic" + SO? + s 3

Iodine is liberated when potassium iodide is added to these salts.

rA

* *

I(I *iii'

Si Jj�j2'

2122]

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U

V

U

a

'aIU

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ii 9 0Pb,

p

E

REFERENCE3 TO TAULE I

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. ..

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I . I

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