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boiling point of any species mainly depends upon 2 fector 1.polerity 2moleculer mass.polerity like as the polerity increases hydrogen bonding also increases.for example we consider HF HCl,HBrHI BP THIS IS HF highest due to hydrogen bonding and high polerity after this moleculer mass comes into play so HI>HBr>HCl.if we examine all the fector in organic chemistry order of boiling point is RCOOH>ROH>RX>ROR>RH these are of comperable moleculer mass so hydrogen bonding and polerity is major fector.in case of diethyl ether and n pentane are of almost same moleculer mass and polerity so bp is close.donot confuse ,ether doesnot have very high dipole moment so less polerity so less boiling point near to alkanes.
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