Phosphorus Compounds - American Chemical Society

36

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Phosphorus Compounds

A

n organic phosphorus compound contains at least one phosphorus atom connected directly or indirectly to the carbon skeleton of the molecule. The phosphorus atom may be a member of an organic chain or ring system, or it may be the central atom in a functional group that is in turn attached to a chain or ring. Although such functional groups commonly have one or more oxygen atoms or OH groups surrounding the phosphorus atom, analogous structures wherein sulfur, selenium, tellurium, or nitrogen (as N H or :N) may be regarded as having replaced oxygen are also considered in this chapter, as are structures wherein halogen or nitrogen (as N H 2 ) has replaced OH. The methods of naming organic phosphorus compounds recommended here may be extended to the corresponding arsenic compounds, but they apply only in part to organic derivatives of antimony and bismuth. :

Recommended Nomenclature Practice Monophosphorus Compounds. PARENT STRUCTURES. Acyclic phosphorus compounds containing only one phosphorus atom, as well as compounds in which each of several phosphorus-containing functional groups contains only a single phosphorus atom, are preferably named as derivatives of the sometimes hypothetical parent structures listed in Table 36.1. When hydrogen attached to phosphorus is replaced by a hydrocarbon group, the derivative is named substitutively.

C H PH 6

5

(CH ) PH 3

2

Phenylphosphine

2

Dimethylphosphorane

3

CH CH CH CH P=0 3

2

2

H (0)PCH CH CH P(0)H 2

2

Butyloxophosphine

2

2

2

2

Trimethylenebis(phosphine oxide)

When hydrogen of an OH group is replaced, the derivative is named radicofunctionally, similarly to esters of carboxylic acids. 278 In Nomenclature of Organic Compounds; Fletcher, J., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

36.

279

Phosphorus Compounds Triethyl phosphate

(CH CH C»3PO 3

2

(C H 0) POCH 6

5

2

(C H ) POCH 6

5

2

Methyl diphenyl phosphite

3

Methyl diphenylphosphinite

3

Dipropyl hydrogen phosphate

(CH CH CH 0) P(0)OH 3

2

2

2

(CH 0) POCH CH OP(OCH )


3

2

2

2

3

2

Ethylene tetramethyl diphosphite

Ionic compounds are named as salts of phosphorus-containing acids or analogously to ammonium compounds {see Chapter 24).

Table 36.1. Phosphorus-Containing Parent Structures Hydrides PH PH

3

Phosphine

H PO

Phosphine oxide

5

Phosphorane

H PS

Phosphine sulfide

H PNH

Phosphine imide

3

3

3

Acids P(OH)

Phosphoric acid

Phosphorous acid

P(0)(OH)

HP(OH)

Phosphonous acid

HP(0)(OH)

Phosphonic acid

H POH

Phosphinous acid

H P(0)OH

Phosphinic acid

0=POH

Phosphenous acid

0=P(0)OH

Phosphenic acid

3

2

2

H POH

3

2

2

fl

Phosphoranoic acid

4

H P(OH) 3

2

H P(OH) 2

Phosphoranedioic acid* fl

3

Phosphoranetrioic acid

HP(OH)

Phosphoranetetroic acid*

P(OH)

Phosphoranepentoic acid*

4

5

Bases and Salts P H OH" +

4

PH

+ 4

cr

Phosphonium hydroxide Phosphonium chloride

(and others containing other anions) ff

These names, though here recommended and prescribed by the 1952 Rules (see Discussion Section), are not recognized by IUPAC and are no longer used by Chemical Abstracts.

In Nomenclature of Organic Compounds; Fletcher, J., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

280

NOMENCLATURE OF ORGANIC COMPOUNDS

(CH CH CH 0) P(0)0 3

2

2

Na

2

+

Sodium dipropyl phosphate

+

(CH CH ) P CF 3

2

Tetraethylphosphonium chloride

4


Acyclic structures containing more than two phosphorus atoms as non-terminal members of an organic chain system are preferably named by replacement nomenclature (see Chapter 7). The prefix phospha denotes a trivalent phosphorus atom.

CH CH PHCH PCH CH NHCH CH PCH PHCH CH 3

2

2

2

I

CH

2

2

2

CH

3

2

I

2

3

3

5,1 l-Dimethyl-8-aza-3,5,11,13-tetraphosphapentadecane Cyclic phosphorus compounds in which one or more phosphorus atoms are members of an organic ring system are preferably named as heterocyclic structures (see Chapter 6).

Phosphabenzene

1,3-Dioxa-2-phosphacyclopentane 2-oxide

HALOGEN DERIVATIVES. If one or more halogen atoms are attached to a phosphorus atom carrying no O H or O R groups, the structure is preferably named as an acid halide. C H PC1 6

5

Pheny lphosphonous dichloride

2

(CH CH ) P(0)Br 3

2

Cl (O)P—^ 2

Diethylphosphinic bromide

2

^—P(0)C1

2

1,4-Phenylenediphosphonic tetrachloride

If, in addition to halogen, a phosphorus atom carries one or more O H and/or O R groups, the structure is preferably named as an acid or ester, and the halogen is designated by the appropriate infix fluorid, chlorid,


36.

Phosphorus Compounds

281

bromid, or to did. An infix beginning with a consonant is preceded by an added o.

CH3POH I I

Methylphosphoniodidous acid

CH CH OP(0)Br


3

2

Ethyl phosphorodibromidate

2

In a like manner, other infixes may be used: cyanatid for OCN, isocyanatid for NCO, nitrid for N (replacing both O and OH simultaneously), and others as specified in the 1952 Rules (1). NITROGEN DERIVATIVES. Compounds having one or more N H groups attached to a phosphorus atom carrying no OH or OR groups are preferably named radicofunctionally as amides. Attachment of substituting groups to phosphorus is denoted by the locant P. 2

( C H ) PNH 6

5

2

P,P-Diphenylphosphinous amide

2

CH P(0)(NH ) 3

2

P-Methylphosphonic diamide

2

If OH and/or OR groups are also attached to the phosphorus atom, the structure is preferably named as an acid or ester by using the appropriate infix amid or diamid. C H„P(0)OH I NH 6

P-Cyclohexylphosphonamidic acid

2

C H OP(NH ) 6

5

2

Phenyl phosphorodiamidite

2

Substituents replacing a hydrogen atom of an N H designated by using the locants N, N', etc. .NHCH C H PNHCH CH

2

group may be

3

6

5

2

3

N-E thyl-N'-methy 1-P-phenylphosphonous diamide

Compounds containing the NH group coordinately bound to a phosphorus atom carrying no OH, OR, or N H groups are preferably named as derivatives of phosphine imide (Table 36.1); if OH and/or OR groups are also present, the structure is named as an acid or ester by using the infix imid; if N H is the only other negative group present, the structure is named as an amide. 2

2


282

NOMENCLATURE OF ORGANIC COMPOUNDS (CH CH CH ) PNH

P,P,P-Tripropylphosphine imide

C H P(NH)(OH)

P-Phenylphosphonimidic acid

3

6

2

2

3

s

2

(CH CH 0) PNH 3

2

Triethyl phosphorimidate

3

C H P(NH)(NH ) 6

S

2

P-Phenylphosphonimidic diamide

2


In assigning locants for groups attached to nitrogen, all N H be considered first, before coordinately bound NH. NHCH CH 2

C H PNCH I NH 6

S

2

groups should

3

#

N-E thyl-AP-methyl-P-phenylphosphonimidic diamide

3

2

SULFUR ANALOGS. Acids and esters in which one or more sulfur atoms are attached to phosphorus are treated as analogs of the corresponding oxygen-containing structures and are preferably named by using the appropriate infix thio, dithio, trithio, or tetrathio. Where required to avoid ambiguity, the locant O or S is placed immediately preceding the part of the name to which it applies. (C H ) P(S)OH 6

s

Diphenylphosphinothioic O-acid

2

CH CH CH CH P(S)(SH)(OH)

Butylphosphonodithioic 0,5-acid

CH CH CH CH P(0)(SH)

Butylphosphonodithioic 5,5-acid

3

2

3

2

2

2

2

2

(CH 0) P(0)SCH CH 3

2

2

5-Ethyl dimethyl phosphorothioate

3

(CH CH S) P 3

2

2

Triethyl phosphorotrithioite

3

Halogen and nitrogen derivatives of phosphorus compounds containing sulfur are treated similarly. When more than one infix is required, these are arranged in alphabetical order. CH CH P(S)Br 3

2

Ethylphosphonothioic dibromide

2

(C H O) P(S)Cl 6

s

(C H ) P(S)NH 6

5

0,0-Diphenyl phosphorochloridothioate .

2

2

P,P-Diphenylphosphinothioic amide

2

CH CH OP(0)(SH)NH 3

2

2

Ethyl S-hydrogen phosphoramidothioate

Compounds in which coordinately bound S is the only atom other than C or H attached to phosphorus are preferably named as derivatives of phosphine sulfide (Table 36.1).


36.

283

Phosphorus Compounds (CH CH CH2)2P(S)H 2

3

Dipropylphosphine sulfide

PHOSPHORUS-CONTAINING SUBSTITUENTS.

When a phosphorus-contain-

ing organic group must be treated as a substituent, a prefix name based on one of the names shown in Table 36.2 should be employed. (CH ) p3

Dimethylphosphino

2

CH CH2CH2PH Downloaded by NORTH CAROLINA STATE UNIV on October 9, 2012 | http://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/ba-1974-0126.ch036

3

3

Propylphosphoranyl

—

(CH CH 0)2P(0)+ (CH ) PCH CH23

3

2

3

2

Diethoxyphosphinyl 2-(Trimethylphosphonio)ethyl

In replacement nomenclature, the phosphonium group is designated by the prefix phosphonia.

CH

3

Cf

1-Methyl-l-phosphonianaphthalene chloride

Table 36.2. Fundamental Phosphorus-Containing Groups H P—

Phosphino

HP—

Phosphinidene

P

Phosphinidyne

2

HP

Phosphoranetetrayl

^P^

Phosphoranepentayl

H f—

Phosphonio

3

H4P—

Phosphoranyl

H (0)P—

Phosphinyl

HP

Phosphoranediyl

H(0)P

Phosphinylidene

H P—

Phosphoranetriyl

(0)P^-

Phosphinylidyne

3

2

2


284

NOMENCLATURE OF ORGANIC COMPOUNDS

H (S)P—

Phosphinothioyl

H (HN)P—

Phosphinimyl

H(S)P

Phosphorus Compounds - American Chemical Society

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